Process for producing aqueous polyacrylamide solutions

ABSTRACT

Process for producing aqueous polyacrylamide solutions by polymerizing an aqueous solution comprising at least acrylamide thereby obtaining an aqueous polyacrylamide gel and dissolving said aqueous polyacrylamide gel in water, wherein the process is carried out in a modular, relocatable plant. The plant preferably is deployed at a location at which aqueous polyacrylamide solutions are used, for example on an oilfield or in a mining area.

The invention relates to a process for producing aqueous polyacrylamidesolutions by polymerizing an aqueous solution comprising at leastacrylamide thereby obtaining an aqueous polyacrylamide gel anddissolving said aqueous polyacrylamide gel in water, wherein the processis carried out in a modular, relocatable plant. The plant preferably isdeployed at a location at which aqueous polyacrylamide solutions areused, for example on an oilfield or in a mining area.

Water-soluble, high molecular weight homo- and copolymers of acrylamidemay be used for various applications such as mining and oilfieldapplications, water treatment, sewage treatment, papermaking, andagriculture. Examples include its use in the exploration and productionof mineral oil, in particular as thickener in aqueous injection fluidsfor enhanced oil recovery or as rheology modifier for aqueous drillingfluids. Further examples include its use as flocculating agent fortailings and slurries in mining activities.

A common polymerization technology for manufacturing such high molecularweight polyacrylamides is the so called “gel polymerization”. In gelpolymerization, an aqueous monomer solution having a relatively highconcentration of monomers, for example from 20% by weight to 35% byweight is polymerized by means of suitable polymerization initiatorsunder essentially adiabatic conditions in an unstirred reactor therebyforming a polymer gel. The polymer gels formed are converted to polymerpowders by comminuting the gel into smaller pieces by one or more sizereduction steps, drying such gel pieces for example in a fluid bed dryerfollowed by sieving, grinding and packaging. The obtained polyacrylamidepowders are thereafter packaged and shipped to customers.

The aqueous polyacrylamide gel obtained from gel polymerizationtypically comprises from 65% to 80% of water. The residual amount ofwater in polyacrylamide powders typically is from about 4 to 12% byweight. So, “drying” such polyacrylamide gels does not mean to removeonly some residual moisture in course of drying but rather about 0.55 to0.75 kg of water need to be removed per kg of polymer gel, or—with otherwords—per kg of polymer powder produced also 1.5 to 2.5 kg of water are“produced”.

It goes without saying that removing such a high amount of water fromthe polymer gels in course of drying is energy extensive andconsequently the operational costs for drying are high. Furthermore,high-performance dryers are necessary as well as equipment for sizereduction, sieving and grinding. Consequently, the capital expenditurefor the entire post-processing equipment including size reduction,drying, sieving, grinding is significant in relation to the totalcapital expenditure for the entire plant.

High-molecular weight polyacrylamides are usually used as dilute aqueoussolutions. Typical concentrations of polyacrylamides for oilfield andmining applications range from 0.05 wt. % to 0.5 wt. %. Consequently,the polyacrylamide powders manufactured as mentioned above need to bedissolved in aqueous fluids before use. Dissolving high molecular weightpolymers in aqueous fluids is time consuming and it is difficult to doso without degrading the polymers and without forming lumps. Suitableequipment for dissolving polyacrylamide powders is necessary on-site.

For oilfield applications, such as enhanced oil recovery or for miningapplications large amounts of polyacrylamides need to be available atone location, i.e. at an oilfield or at a mining area. By way ofexample, even for flooding only a medium size oilfield it may benecessary to inject some thousand m³ of polymer solution per day intothe oil-bearing formation and usually the process of polymer floodingcontinues for months or even years. So, for a polymer concentration ofonly 0.2 wt. % and an injection rate of 5000 m³/day 10 t of polymerpowder are needed per day and need to be dissolved in an aqueous fluid.

It has been suggested not to dry the aqueous polyacrylamide gels aftermanufacture but directly dissolving said polyacrylamide gels in waterthereby obtaining diluted aqueous solutions of polyacrylamides withoutdrying and re-dissolving the dry powder. Working in such a manner savescapital expenditures and operational costs for drying and furtherpost-processing. However, shipping dilute aqueous solutions ofpolyacrylamides to customers is not an option because transport costsbecome extremely high as compared to transporting powders. It hastherefore been suggested to manufacture aqueous polyacrylamide solutionson-site.

DE 2 059 241 discloses a process for preparing water-soluble polymers,including acrylamide containing polymers, in which an aqueous solutioncomprising water-soluble monomers and polymerization initiators isfilled into transportable containers for polymerization. In thetransportable containers, the aqueous solution polymerizes therebyforming polymer gel. The gel may be transported to the end users who canremove the polymer gels and dissolve them in water. The transportablecontainers may be—for instance—bags, cans, drums, or boxes having avolume from 2 l to 200 l.

U.S. Pat. No. 4,248,304 discloses a process for recovering oil fromsubterranean formations wherein a water-in-oil-emulsion of an acrylamidepolymer in the presence of an inverting agent is injected into theformation. The water-in-oil emulsion is manufactured in a small chemicalplant located near the wells and the manufacturing procedure comprisesthe steps of forming a water-in-oil emulsion of acrylonitrile,converting a substantially portion of the acrylonitrile to acrylamideusing a suitable catalyst, and polymerizing the water-in-oil emulsion ofacrylamide in the presence of a free radical polymerization catalyst.The catalyst may be a copper catalyst.

ZA 8303812 discloses a process for preparing polyacrylamides comprisingpolymerizing acrylamide and optionally suitable comonomers on-site andtransferring the polymer formed to its desired place of use on sitewithout drying or concentrating. The polymerization can be carried outas an emulsion polymerization, bead polymerization, or assolution/dispersion polymerization. The polymer may be pumped from thepolymerization reactor to the position on site where it is used.

WO 84/00967 A1 discloses an apparatus and method for the continuousproduction of aqueous polymer solutions, in particular partiallyhydrolyzed polyacrylamide. The apparatus comprises a polymerizationreactor, a hydrolysis reactor and a diluter. The polymerization may beperformed on-site and the solutions may be used in secondary or tertiaryoil recovery.

U.S. Pat. No. 4,605,689 discloses a method for on-site production ofaqueous polyacrylamide solutions for enhanced oil recovery. In a firststep an aqueous polyacrylamide gel is provided by polymerizingacrylamide and preferably acrylic acid as comonomer. The polyacrylamidegel obtained is conveyed together with a minor amount of aqueous solventthrough at least one static cutting device thereby obtaining a slurry ofsmall gel particles in water, the gel particles are dissolved in theaqueous solvent which forms a homogeneous solution concentrate which isthen readily diluted with aqueous solvent thereby obtaining a dilutedaqueous polyacrylamide solution.

U.S. Pat. No. 4,845,192 discloses a method of rapidly dissolvingparticles of gels of water-soluble polymers comprising forming asuspension of such gel particles in water and subjecting said suspensionto instantaneous and momentary conditions of high shearing effective tofinely slice said particles.

Our older application WO 2017/186567 A1 relates to a process forproducing an aqueous polymer solution comprising the steps of providingan aqueous polyacrylamide gel comprising at least 10% by weight ofactive polymer, cutting the aqueous polyacrylamide gel by means of awater-jet at a pressure of at least 150 bar to reduce the size of theaqueous polyacrylamide gel, and dissolving the aqueous polyacrylamidegel in an aqueous liquid.

Our older application WO 2017/186697 A1 relates to a method of preparingan aqueous polyacrylamide solution, comprising hydrolyzing acrylonitrilein water in presence of a biocatalyst thereby obtaining an acrylamidesolution, directly polymerizing the acrylamide solution therebyobtaining a polyacrylamide gel, and directly dissolving thepolyacrylamide gel by addition of water thereby obtaining an aqueouspolyacrylamide solution. The method may be carried out on-site.

Our older application WO 2017/186685 A1 relates to a method of preparingan aqueous polyacrylamide solution, comprising hydrolyzing acrylonitrilein water in presence of a biocatalyst thereby obtaining an acrylamidesolution, directly polymerizing the acrylamide solution therebyobtaining a polyacrylamide gel, and directly dissolving thepolyacrylamide gel by addition of water by means of a mixer comprising arotatable impeller thereby obtaining an aqueous polyacrylamide solution.The method may be carried out on-site.

Our older application WO 2017/186698 A1 relates to a method of preparingan aqueous polyacrylamide solution, comprising hydrolyzing acrylonitrilein water in presence of a biocatalyst thereby obtaining an acrylamidesolution, directly polymerizing the acrylamide solution therebyobtaining a polyacrylamide gel, and directly dissolving thepolyacrylamide gel by addition of water by means of water-jet cutting,thereby obtaining an aqueous polyacrylamide solution. The method may becarried out on-site.

WO 2016/006556 A1 describes a method for producing a compound using acontinuous tank reactor which is provided with two or more reactiontanks for producing the compound and with a reaction liquid feeding pipethat feeds a reaction liquid from an upstream reaction tank to adownstream reaction tank, said method being characterized in that theReynold's number of the reaction liquid that flows in the reactionliquid feeding pipe is configured to be 1800-22000. The tank reactor maybe mounted in a portable container. The compound may be acrylamideproduced by conversion from acrylonitrile by means of a biocatalyst.

WO 2017/167803 A1 discloses a method for producing a polyacrylamidesolution having an increased viscosity by preparing an aqueousacrylamide solution by converting acrylonitrile to acrylamide using abiocatalyst, separating the biocatalyst from the aqueous acrylamidesolution such that the OD600 of the aqueous acrylamide solution is equalor less than 0.6, and polymerizing the aqueous acrylamide solution thusobtained to polyacrylamide.

WO 97/21827 A1 discloses a process for making a solution of ammoniumacrylate by enzymatic hydrolysis of acrylonitrile.

The production of polyacrylamide solution on-site saves equipment andoperational costs for drying and re-dissolving of polyacrylamides on theone hand. On the other hand, the need of polyacrylamide solutions at onesite can be limited in time. By the way of example, in enhanced oilrecovery operations, aqueous solutions of polyacrylamides may beinjected into the subterranean formations for months or even a fewyears, however usually for no longer time. When the polyacrylamidesolutions are no longer needed at one site, it is necessary to transportdiluted aqueous solutions to another site which generates high transportcosts. Deconstructing the plant at the original site and erecting it atanother site may also be connected with high costs.

It was an object of the present invention to provide an improved processfor manufacturing aqueous solutions of polyacrylamides on-site using aplant capable of becoming relocated easily.

Accordingly, in one embodiment of the present invention, a process forproducing an aqueous polyacrylamide solution by polymerizing an aqueoussolution comprising at least acrylamide thereby obtaining an aqueouspolyacrylamide gel and dissolving said aqueous polyacrylamide gel inwater has been found, wherein the process is conducted in a modular,relocatable plant and the process comprises at least the followingsteps:

-   -   [1] Preparing—in a relocatable monomer make-up unit—an aqueous        monomer solution comprising at least water and 5% to 45% by        weight—relating to the total of all components of the aqueous        monomer solution—of water-soluble, monoethylenically unsaturated        monomers, wherein said water-soluble, monoethylenically        unsaturated monomers comprise at least acrylamide    -   [2] Inerting and radically polymerizing the aqueous monomer        solution prepared in step [1] in the presence of suitable        initiators for radical polymerization under adiabatic        conditions, wherein        -   the polymerization is performed in a relocatable            polymerization unit having a volume of 1 m³ to 100 m³,        -   the aqueous monomer solution has a temperature T1 not            exceeding 30° C. before the onset of polymerization, and        -   the temperature of the polymerization mixture raises in            course of polymerization—due to the polymerization heat            generated- to a temperature T2 of at least 45° C.,    -   thereby obtaining an aqueous polyacrylamide gel having a        temperature T2 which is hold in the relocatable polymerization        unit,    -   [3] removing the aqueous polyacrylamide gel from the relocatable        polymerization unit,    -   [4] comminuting the aqueous polyacrylamide gel by conveying the        aqueous polyacrylamide gel through at least one comminuting        unit, thereby obtaining aqueous polyacrylamide gel pieces,    -   [5] and dissolving the aqueous polyacrylamide gel pieces in an        aqueous liquid in a relocatable dissolution unit, thereby        obtaining an aqueous polyacrylamide solution.

In a preferred embodiment, the process comprises an additional step [0]comprising hydrolyzing acrylonitrile in water in the presence of abiocatalyst capable of converting acrylonitrile to acrylamide in arelocatable bioconversion unit, thereby obtaining an aqueous acrylamidesolution, and wherein said aqueous acrylamide solution is used for step[1].

In another embodiment, the present invention relates to a process forproducing an aqueous polyacrylamide solution by polymerizing an aqueoussolution comprising at least acrylamide thereby obtaining an aqueouspolyacrylamide gel and dissolving said aqueous polyacrylamide gel inwater has been found, wherein the process is conducted in a modular,relocatable plant and the process comprises at least the followingsteps:

-   -   [0] Hydrolyzing acrylonitrile in water in the presence of a        biocatalyst capable of converting acrylonitrile to acrylamide,        thereby obtaining an aqueous acrylamide solution,    -   [1] Preparing—in a relocatable monomer make-up unit—an aqueous        monomer solution comprising at least water and 15% to 24.9% by        weight—relating to the total of all components of the aqueous        monomer solution—of water-soluble, monoethylenically unsaturated        monomers, wherein said water-soluble, monoethylenically        unsaturated monomers comprise at least acrylamide    -   [2] Inerting and radically polymerizing the aqueous monomer        solution prepared in step [1] in the presence of suitable        initiators for radical polymerization under adiabatic        conditions, wherein        -   the polymerization is performed in a relocatable            polymerization unit having a volume of 1 m³ to 100 m³,        -   the aqueous monomer solution has a temperature T1 from            −5° C. to +5° C. before the onset of polymerization, and        -   the temperature of the polymerization mixture raises in            course of polymerization—due to the polymerization heat            generated- to a temperature T2 from 50 to 70° C.,    -   thereby obtaining an aqueous polyacrylamide gel which is hold in        the relocatable polymerization unit,    -   [3] removing the aqueous polyacrylamide gel from the relocatable        polymerization unit,    -   [4] comminuting the aqueous polyacrylamide gel by conveying the        aqueous polyacrylamide gel through at least one comminuting        unit, thereby obtaining aqueous polyacrylamide gel pieces,    -   [5] and dissolving the aqueous polyacrylamide gel pieces in an        aqueous liquid in a relocatable dissolution unit, thereby        obtaining an aqueous polyacrylamide solution.

In another embodiment, the invention relates to a modular, relocatableplant for manufacturing aqueous polyacrylamide solutions by polymerizingan aqueous solution comprising at least acrylamide thereby obtaining anaqueous polyacrylamide gel and dissolving said aqueous polyacrylamidegel in water, comprising at least

-   -   a relocatable storage unit for an aqueous acrylamide solution,    -   optionally relocatable storage units for water-soluble,        monoethylenically unsaturated monomers different from        acrylamide,    -   a relocatable storage unit for polymerization initiators,    -   a relocatable monomer make-up unit for preparing an aqueous        monomer solution comprising at least water and acrylamide,    -   a relocatable polymerization unit for polymerizing the aqueous        monomer solution in the presence of polymerization initiators,    -   a relocatable comminution unit for comminuting aqueous        polyacrylamide gel to pieces of aqueous polyacrylamide gel,    -   a relocatable dissolution unit for the dissolution of pieces of        aqueous polyacrylamide gel in aqueous fluids.

Preferably, the plant additionally comprises the following units:

-   -   a relocatable storage unit for acrylonitrile,    -   a relocatable bioconversion unit for hydrolyzing acrylonitrile        in water in the presence of a biocatalyst capable of converting        acrylonitrile to acrylamide,    -   a relocatable unit for removing the biocatalyst from an aqueous        acrylamide solution.

In another embodiment, the plant the modular, relocatable plant isdeployed at a location at which the polyacrylamide solutions are used,for example on an oilfield or in a mining area.

LIST OF FIGURES

FIG. 1 Schematic representation of a storage unit for monomers withinternal temperature control unit. FIG. 2 Schematic representation of astorage unit for monomers with external temperature control unit. FIG. 3Schematic representation of a bio acrylamide reactor. FIG. 4 Schematicrepresentation of a monomer make-up unit. FIG. 5 Schematicrepresentation of a relocatable polymerization unit P1. FIG. 6 Schematicrepresentation of a relocatable polymerization unit P1 connected withcomminution unit. FIG. 7 Schematic representation of a water-jet cuttingunit. FIG. 8 Schematic representation of another embodiment of awater-jet cutting unit. FIG. 9 Schematic representation of anotherembodiment of a water-jet cutting unit. FIG. 10 Schematic representationof another embodiment of a water-jet cutting unit. FIG. 11 Schematicrepresentation of a water-jet cutting unit comprising additionallystatic cutting units. FIG. 12 Schematic representation of a water-jetcutting unit combined with a hole perforation plate (one nozzle). FIG.13 Schematic representation of a water-jet cutting unit combined with ahole perforation plate (more than one nozzles). FIG. 14 Schematicrepresentation of a water-jet cutting unit combined with a holeperforation plate (one nozzle). FIG. 15 Schematic representation of awater-jet cutting unit combined with a hole perforation plate (more thanone nozzles). FIG. 16 Schematic representation of a water-jet cuttingunit combined with a knife. FIG. 17 Schematic representation of adissolution unit comprising one dissolution vessel. FIG. 18 Schematicrepresentation of a dissolution unit comprising two dissolution vessels.

With regard to the invention, the following can be stated specifically:

By means of the process according to the present invention, it ispossible to prepare aqueous solutions of polyacrylamides.

Polyacrylamides

The term “polyacrylamides” as used herein means water-solublehomopolymers of acrylamide, or water-soluble copolymers comprising atleast 10%, preferably at least 20%, and more preferably at least 30% byweight of acrylamide and at least one additional water-soluble,monoethylenically unsaturated monomer different from acrylamide, whereinthe amounts relate to the total amount of all monomers in the polymer.Copolymers are preferred.

The term “water-soluble monomers” in the context of this invention meansthat the monomers are to be soluble in the aqueous monomer solution tobe used for polymerization in the desired use concentration. It is thusnot absolutely necessary that the monomers to be used are miscible withwater without any gap; instead, it is sufficient if they meet theminimum requirement mentioned. It is to be noted that the presence ofacrylamide in the monomer solution might enhance the solubility of othermonomers as compared to water only. In general, the solubility of thewater-soluble monomers in water at room temperature should be at least50 g/I, preferably at least 100 g/I.

Basically, the kind and amount of water-soluble, monoethylenicallyunsaturated comonomers to be used besides acrylamide is not limited anddepends on the desired properties and the desired use of the aqueoussolutions of polyacrylamides to be manufactured.

Neutral Comonomers

In one embodiment of the invention, comonomers may be selected fromuncharged water-soluble, monoethylenically unsaturated monomers.Examples comprise methacrylamide, N-methyl(meth)acrylamide,N,N′-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide orN-vinylpyrrolidone. Further examples have been mentioned in WO2015/158517 A1 page 7, lines 9 to 14.

Anionic Comonomers

In a further embodiment of the invention, comonomers may be selectedfrom water-soluble, monoethylenically unsaturated monomers comprising atleast one acidic group, or salts thereof. The acidic groups arepreferably selected from the group of —COOH, —SO₃H and —PO₃H₂ or saltsthereof. Preference is given to monomers comprising COOH groups and/or—SO₃H groups or salts thereof. Suitable counterions include especiallyalkali metal ions such as Li⁺, Na⁺ or K⁺, and also ammonium ions such asNH₄ ⁺ or ammonium ions having organic radicals. Examples of ammoniumions having organic radicals include [NH(CH₃)₃]⁺, [NH₂(CH₃)₂]⁺,[NH₃(CH₃)]⁺, [NH(C₂H₅)₃]⁺, [NH₂(C₂H₅)₂]⁺, [NH₃(C₂H₅)]⁺,[NH₃(CH₂CH₂OH)]⁺, [H₃N—CH₂CH₂—NH₃]²⁺ or [H(H₃C)₂N—CH₂CH₂CH₂NH₃]²⁺.

Examples of monomers comprising —COOH groups include acrylic acid,methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaricacid or salts thereof. Preference is given to acrylic acid or saltsthereof.

Examples of monomers comprising —SO₃H groups or salts thereof includevinylsulfonic acid, allylsulfonic acid,2-acrylamido-2-methylpropanesulfonic acid (ATBS),2-methacrylamido-2-methylpropanesulfonic acid,2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonicacid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid. Preference isgiven to 2-acrylamido-2-methylpropanesulfonic acid (ATBS) or saltsthereof.

Examples of monomers comprising—PO₃H₂ groups or salts thereof includevinylphosphonic acid, allylphosphonic acid,N-(meth)acrylamidoalkylphosphonic acids or(meth)acryloyloxyalkyl-phosphonic acids, preferably vinylphosphonicacid.

Preferred monomers comprising acidic groups comprise acrylic acid and/orATBS or salts thereof.

Cationic Comonomers

In a further embodiment of the invention, comonomers may be selectedfrom water-soluble, monoethylenically unsaturated monomers comprisingcationic groups. Suitable cationic monomers include especially monomershaving ammonium groups, especially ammonium derivatives ofN-(ω-aminoalkyl)(meth)acrylamides or ω-aminoalkyl (meth)acrylates suchas 2-trimethylammonioethyl acrylate chloride H₂C═CH—CO—CH₂CH₂N⁺(CH₃)₃Cl⁻(DMA3Q). Further examples have been mentioned in WO 2015/158517 A1 page8, lines 15 to 37. Preference is given to DMA3Q.

Associative Comonomers

In a further embodiment of the invention, comonomers may be selectedfrom associative monomers.

Associative monomers impart hydrophobically associating properties topolyacrylamides.

Associative monomers to be used in the context of this invention arewater-soluble, monoethylenically unsaturated monomers having at leastone hydrophilic group and at least one, preferably terminal, hydrophobicgroup. Examples of associative monomers have been described for examplein WO 2010/133527, WO 2012/069478, WO 2015/086468 or WO 2015/158517.

“Hydrophobically associating copolymers” are understood by a personskilled in the art to mean water-soluble copolymers which, as well ashydrophilic units (in a sufficient amount to assure water solubility),have hydrophobic groups in lateral or terminal positions. In aqueoussolution, the hydrophobic groups can associate with one another. Becauseof this associative interaction, there is an increase in the viscosityof the aqueous polymer solution compared to a polymer of the same kindthat merely does not have any associative groups.

Examples of suitable associative monomers comprise monomers having thegeneral formula H₂C═C(R¹)—R²-R³ (I) wherein R¹ is H or methyl, R² is alinking hydrophilic group and R³ is a terminal hydrophobic group.Further examples comprise having the general formula H₂C═C(R¹)—R²-R³-R⁴(II) wherein R¹, R² and R³ are each as defined above, and R⁴ is ahydrophilic group.

The linking hydrophilic R² group may be a group comprising ethyleneoxide units, for example a group comprising 5 to 80 ethylene oxideunits, which is joined to the H₂C═C(R¹)— group in a suitable manner, forexample by means of a single bond or of a suitable linking group. Inanother embodiment, the hydrophilic linking group R² may be a groupcomprising quaternary ammonium groups.

In one embodiment, the associative monomers are monomers of the generalformula H₂C═C(R¹)—O—(CH₂CH₂O)_(k)—R^(3a) (III) orH₂C═C(R⁵)—(C═O)—O—(CH₂CH₂O)_(k)—R^(3a) (IV), wherein R¹ has the meaningdefined above and k is a number from 10 to 80, for example, 20 to 40.R^(3a) is an aliphatic and/or aromatic, straight-chain or branchedhydrocarbyl radical having 8 to 40 carbon atoms, preferably 12 to 32carbon atoms. Examples of such groups include n-octyl, n-decyl,n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl groups. In a furtherembodiment, the groups are aromatic groups, especially substitutedphenyl radicals, especially distyrylphenyl groups and/or tristyrylphenylgroups.

In another embodiment, the associative monomers are monomers of thegeneral formulaH₂C═C(R¹)—O—(CH₂)_(n)—O—(CH₂CH₂O)_(x)—(CH₂—CH(R⁵)O)_(y)—(CH₂CH₂O)_(z)H(V), wherein R¹ is defined as above and the R⁵ radicals are eachindependently selected from hydrocarbyl radicals comprising at least 2carbon atoms, preferably from ethyl or propyl groups. In formula (V) nis a natural number from 2 to 6, for example 4, x is a number from 10 to50, preferably from 12 to 40, and for example, from 20 to 30 and y is anumber from 5 to 30, preferably 8 to 25. In formula (V), z is a numberfrom 0 to 5, for example 1 to 4, i.e. the terminal block of ethyleneoxide units is thus merely optionally present. In an embodiment of theinvention, it is possible to use at least two monomers (V), wherein theR¹ and R⁶ radicals and indices n, x and y are each the same, but in oneof the monomers z=0 while z>0 in the other, preferably 1 to 4.

In another embodiment, the associative monomers are cationic monomers.Examples of cationic associative monomers have been disclosed in WO2015/158517 A1, page 11, line 20 to page 12, lines 14 to 42. In oneembodiment, the cationic monomers having the general formulaH₂C═C(R¹)—C(═O)O—(CH₂)_(k)—N+(CH₃)(CH₃)(R⁶) X⁻ (VI) orH₂C═C(R¹)—C(═O)N(R¹)—(CH₂)_(k)—N⁺ (CH₃)(CH₃)(R⁶) X⁻ (VII) may be used,wherein R¹ has the meaning as defined above, k is 2 or 3, R⁶ is ahydrocarbyl group, preferably an aliphatic hydrocarbyl group, having 8to 18 carbon atoms, and X⁻ is a negatively charged counterion,preferably Cl⁻ and/or Br⁻.

Further Comonomers

Besides water-soluble monoethylenically unsaturated monomers, alsowater-soluble, ethylenically unsaturated monomers having more than oneethylenic group may be used. Monomers of this kind can be used inspecial cases in order to achieve easy crosslinking of the acrylamidepolymers. The amount thereof should generally not exceed 2% by weight,preferably 1% by weight and especially 0.5% by weight, based on the sumtotal of all the monomers. More preferably, the monomers to be used inthe present invention are only monoethylenically unsaturated monomers.

Composition of Polyacrylamides

The specific composition of the polyacrylamides to be manufacturedaccording the process of the present invention may be selected accordingto the desired use of the polyacrylamides.

Preferred polyacrylamides comprise, besides at least 10% by weight ofacrylamide, at least one water-soluble, monoethylenically unsaturatedcomonomer, preferably at least one comonomer selected from the group ofacrylic acid or salts thereof, ATBS or salts thereof, associativemonomers, in particular those of formula (V) or DMA3Q, more preferablyat least one comonomer selected from acrylic acid or salts thereof, ATBSor salts thereof, associative monomers, in particular those of formula(V).

In one embodiment, the polyacrylamides comprise 20% to 90% by weight ofacrylamide and 10% to 80% by weight of acrylic acid and/or saltsthereof, wherein the amounts of the monomers relate to the total of allmonomers in the polymer.

In one embodiment, the polyacrylamides comprise 20% to 40% by weight ofacrylamide and 60% to 80% by weight of acrylic acid and/or saltsthereof.

In one embodiment, the polyacrylamides comprise 55% to 75% by weight ofacrylamide and 25% to 45% by weight of acrylic acid and/or saltsthereof.

In one embodiment, the polyacrylamides comprise 45% to 75% by weight ofacrylamide and 25% to 55% by weight of ATBS and/or salts thereof.

In one embodiment, the polyacrylamides comprise 30% to 80% by weight ofacrylamide, 10% to 40% by weight of acrylic acid and/or salts thereof,and 10% to 40% by weight of ATBS and/or salts thereof.

In one embodiment, the polyacrylamides comprise 45% to 75% by weight ofacrylamide, 0.1 to 5%, preferably 0.1 to 2% by weight of at least oneassociative monomer of the general formulas (I) or (II) mentioned aboveand 10 to 54.9% by weight of acrylic acid and/or ATBS and/or saltsthereof. Preferably, the associative monomer(s) have the general formula(V) including the preferred embodiments mentioned above.

In one embodiment, the polyacrylamides comprise 60% to 75% by weight ofacrylamide, 0.1 to 5%, preferably 0.1 to 2% by weight of at least oneassociative monomer of the general formula (V) mentioned above,including the preferred embodiments, and 20 to 39.9% by weight ofacrylic acid or salts thereof.

In one embodiment, the polyacrylamides comprise 45% to 55% by weight ofacrylamide, 0.1 to 5%, preferably 0.1 to 2% by weight of at least oneassociative monomer of the general formula (V) mentioned above,including the preferred embodiments, and 40 to 54.9% by weight ofacrylic acid or salts thereof.

In one embodiment, the polyacrylamides comprise 60% to 99% by weight ofacrylamide and 1% to 40% by weight of DMA3Q.

In one embodiment, the polyacrylamides comprise 10% to 50% by weight ofacrylamide and 50% to 90% by weight of DMA3Q.

In one embodiment, the polyacrylamides comprise 90 to 99.5% by weight ofacrylamide, 0.5 to 2% by weight of at least one associative monomer, and0% to 9.5% by weight of and anionic monomer, for example ATBS or acationic monomer, for example DM3AQ. Preferably, the associativemonomer(s) have the general formula (V) including the preferredembodiments mentioned above.

In all embodiments mentioned above, the amount of the monomers relatesto the total of all monomers in the polyacrylamide. Furtherwater-soluble, monoethylenically unsaturated monomers may be presentbesides those specifically mentioned, however, the embodiments eachinclude also one embodiment in which besides the monomers specificallymentioned no further monomers are present, i.e. the total amount of themonomers specifically mentioned is 100% by weight.

The weight average molecular weight M_(w) of the polyacrylamides to bemanufactured usually ranges from 1*10⁶ g/mol to 50*10⁶ g/mol, preferablyfrom 1.5*10⁶ g/mol to 40*10⁶ g/mol, more preferably from 2*10⁶ g/mol to30*10⁶ g/mol, and for example from 5*10⁶ g/mol to 25*10⁶ g/mol.

Modular Plant Comprising Relocatable Units

The plant according to the present invention is a modular, relocatableplant comprising several relocatable units. Each relocatable unitbundles certain functions of the plant. Examples of such relocatableunits comprise units for storing and optionally cooling the monomers andother raw materials, hydrolyzing acrylonitrile, mixing monomers,polymerization and gel dissolution. Details will be provided below. Forperforming the process according to the present invention individualunits are connected with each other in a suitable manner therebyobtaining a production line.

“Relocatable unit” means that the unit is not permanently fixed with theground but is transportable to another location. It is transportablebasically as a whole and that is it not necessary to disassemble theentire unit into individual parts for transport. Transport may happen ontrucks, railcars or ships.

Such a modular composition of the plant enables an easy relocation ofthe plant from one location to another location. As will be detailedbelow, the plant may be deployed at sites at which aqueouspolyacrylamide solutions are needed or close to such sites. When thereis no longer a need for aqueous polyacrylamide solutions at such a sitethe plant may become relocated to another site at which there is a needfor polyacrylamide solutions.

In one embodiment, such modular, relocatable units are containerizedunits which may be transported in the same manner as closed intermodalcontainers for example on trucks, railcars or ships. Intermodalcontainers are large standardized (according to ISO 668) shippingcontainers, in particular designed and built for intermodal freighttransport. Such containers are also known as ISO containers. Such ISOcontainers may have external dimensions of a height of ˜2.59 m, a widthof ˜2.44 m and a length of ˜6.05 m. Larger ISO containers have externaldimensions of a height of ˜2.59 m, a width of ˜2.44 m and a length of˜12.19 m.

In another embodiment, the relocatable units may be fixed on trucks oron trailers. With other words, for such relocatable units not acontainer or something similar is deployed at the site of the modularplant, but the entire truck or the trailer including the unit in itsloading spaces is deployed. The trucks or trailers advantageously alsofunction as platform for the units on the ground. Also, two or moredifferent units may be mounted together on a truck or trailer.

The modular, relocatable plant for preparing polyacrylamide solutionsaccording to the present invention basically may be deployed at anylocation. From such a location, the polyacrylamide solutions may betransported to the locations at which the polyacrylamide solutions areused.

However, preferably the plant is deployed at a location at which thepolyacrylamide solutions are used or at least a location close to such alocation of use.

In one embodiment, the modular, relocatable plant may be deployed at anoil and/or gas well to be treated with aqueous polyacrylamide solutionsor close to such an oil and/or gas well.

Examples comprise oil wells which into which aqueous polyacrylamidesolutions are injected in course of enhanced oil operations, productionwells whose productivity is enhanced by injection of fracturing fluidscomprising polyacrylamides as friction reducers, or wells which aredrilled and aqueous polyacrylamide solutions are used for making thedrilling fluid. In another embodiment, the plant may be deployed inbetween a plurality of such oil and/or gas wells or at one of them andthe aqueous polyacrylamide solution is distributed to all injectionwells, for example by means of pipelines.

In the field of mining, the modular, relocatable plant may be a locationat or close to a tailings ponds in which mineral tailings are dewateredusing aqueous polyacrylamide solutions. In one embodiment of theinvention, it may be a location for the treatment of red mud, aby-product of the Bayer process for manufacturing aluminium.

In other embodiments, the location may be at a paper production site, atsewage works or at seawater desalination plants or at sites formanufacturing agricultural formulations.

The distance between the location of the modular, relocatable plant andthe location at which polyacrylamide is used is not specificallylimited. However, in order to limit the costs of transporting theaqueous polyacrylamide solutions the location of the plant and thelocation of using the polyacrylamide should not be too far apart fromeach other. By the way of example, the distance between location of themodular, relocatable plant and the location(s) of using polyacrylamidesolutions may range from 0.1 to 500 km, for example from 0.1 to 100 km,from 0.2 to 10 km or from 0.5 to 5 km.

Provision of Acrylamide

Acrylamide may be synthesized by partial hydrolysis of acrylonitrileusing suitable catalysts. It is known in the art to use copper catalystsor other metal containing catalysts and it is also known to usebiocatalysts capable of converting acrylonitrile to acrylamide. Pureacrylamide is a solid, however, typically acrylamide—whether made by biocatalysis or copper catalysis—is provided as aqueous solution, forexample as aqueous solution comprising about 50% by wt. of acrylamide.

Acrylamide obtained by means of biocatalysts (often referred to as “bioacrylamide”) can be distinguished from acrylamide obtained by means ofcopper catalysts or other metal containing catalysts because the latterstill comprises at least traces of copper or other metals. Acrylamideobtained by means of biocatalysts may still comprise traces of thebiocatalyst.

For the process according to the present invention, preferably anaqueous acrylamide solution is used which has been obtained byhydrolyzing acrylonitrile in water in presence of a biocatalyst capableof converting acrylonitrile to acrylamide. As will be detailed below,using biocatalysts for hydrolyzing acrylonitrile has significantadvantages for the present invention.

In one embodiment of the invention, aqueous solutions of bio acrylamidefor use in the process according to the present invention may bemanufactured at another location, and shipped to the location of themodular, relocatable plant according to the present invention.

Such other location of manufacture may be at a fixed chemical plant or amodular, relocatable plant for the manufacture of bio-acrylamide atanother location than the plant according to the present invention. Amodular, relocatable plant for the manufacture of bio acrylamide may belocated closer—as compared to a fixed chemical plant—to the modular,relocatable plant according to the present invention, for example in amining area or at an oilfield, thereby minimizing transport costs. Fromsuch a location one or more than one modular plants for the manufactureof aqueous polyacrylamide solutions according to the present inventionmay be served with bio acrylamide. In one embodiment, the site ofmanufacture of bio acrylamide may be apart 1 to 200 km from the modular,relocatable plant according to the present invention.

In a preferred embodiment of the present invention the manufacture ofbio acrylamide is also performed by the modular, relocatable plantaccording to the present invention by means of a suitable bioconversionunit (hereinafter designated as process step [0]).

Manufacturing bio acrylamide by the modular, relocatable plant savessignificant transport costs. Acrylonitrile is a liquid and may betransported as pure compound to the location of the plant. The molecularweight of acrylamide is ˜34% higher than that of acrylonitrile andacrylamide is typically provided as ˜50% aqueous solution. So, for a 50%aqueous solution of acrylamide the mass to be transported is about2.5-fold as much as compared to transporting pure acrylonitrile.Transporting pure, solid acrylamide means transporting only ˜34% moremass as compared to transporting pure acrylonitrile, however, additionalequipment for handling and dissolving the solid acrylamide is necessaryat the location of the plant.

Step [0]—Hydrolysis of Acrylonitrile

As already outlined above, step [0] is only optional for the processaccording to the present invention, however, in a preferred embodimentof the invention, the process according to the invention includes step[0]. In course of step [0] acrylonitrile is hydrolyzed in water inpresence of a biocatalyst capable of converting acrylonitrile toacrylamide thereby obtaining an aqueous acrylamide solution.

Provision of Acrylonitrile

Acrylonitrile for step [0] may be stored in one or more than onerelocatable storage units. The storage unit comprises a storage vessel.The volume of the storage vessel is not specifically limited and mayrange from 50 m³ to 150 m³, for example it may be about 100 m³.Preferably, the storage vessel should be double walled and should behorizontal. Such a construction avoids installing a pit for thecollection of any leakage thereby ensuring an easier and quickerrelocation of the storage unit. Double-walled vessels may be placed onevery good bearing soil. The storage unit furthermore comprises meansfor charging and discharging the vessel, means for controlling thepressure in the vessel, for example a valve for settling low-pressure oroverpressure,

and means for controlling the temperature of the acrylonitrile whichpreferably should not exceed 25° C. It furthermore may comprise meansfor measurement and control to the extent necessary.

Examples of relocatable storage units comprise relocatable cuboid,storage tanks, preferably double-walled tanks. Further, any considerableform, shape and size of container is suitable and applicable for thestorage and/or provision of acrylonitrile in the sense of the presentinvention. Particularly, standard iso-tanks are applicable for thestorage and/or provision of acrylonitrile.

Other examples comprise tank containers having a cuboid frame,preferably a frame according to the ISO 668 norm mentioned above and oneor more storage vessels mounted into the frame. Such normed tankcontainers may be stacked and transported on trucks, railcars or shipsin the same manner closed intermodal containers.

Basically, temperature control may be performed by any kind oftemperature controlling unit. Temperature control may require—dependingon the climatic conditions prevailing at the site of the modularplant—cooling or heating the contents of the storage units. Regardingthe monomers, temperature control typically means cooling, because itshould be avoided that the monomers become too hot. In one embodiment,an internal heat exchanger may be used for cooling or heating, i.e. aheat exchanger mounted inside of the storage vessel. The coolant isprovided to the heat exchanger by a suitable cooling or heating unitmounted outside of the storage vessel. In another embodiment of theinvention, for temperature control an external temperature controlcycle, for example a cooling cycle is used, which comprises a pump whichpumps the monomer from the storage vessel through a heat exchanger andback into the storage vessel.

The temperature control cycle may be a separate, relocatable temperaturecontrol unit comprising pump and heat exchanger and which is connectedwith the storage vessel by pipes or flexible tubes.

In another embodiment, the temperature control cycle may be integratedinto relocatable storage unit. It may—for example—be located at one endof the unit besides the storage vessel.

FIG. 1 schematically represents one embodiment of a monomer storage unitcomprising an integrated temperature control cycle. It comprises a frame(1). The frame may in particular be a cuboid frame preferably havingstandardized container dimensions which eases transport. The relocatablestorage unit furthermore comprises a double-walled vessel mounted intothe frame comprising an outer wall (2) and an inner wall (3). In otherembodiments, there is no such frame (1) but the storage vessel isself-supporting. The storage vessel is filled with acrylonitrile. Thestorage unit furthermore comprises an external temperature control cyclecomprising at least a pump and a temperature control unit. For cooling,acrylonitrile is circulated by means of a pump (4) from the storagevessel to the temperature control unit (5) and back into the storagevessel. The amount of acrylonitrile to be circulated in the temperaturecontrol cycle in order to control the temperature at an acceptablelevel, for example below 25° C. depends in particular on the outsidetemperature and the internal temperature envisaged. In one embodiment,10% to 100% of the volume of acrylonitrile in the vessel may becirculated per hour.

FIG. 2 represents a schematically another embodiment of a monomerstorage unit. It comprises a cuboic, preferably double-walled storagevessel (6). If necessary, the storage vessel (6) is connected with anexternal, relocatable temperature control unit (7).

Acrylonitrile may be provided to the site of the modular plant by roadtankers, ISOtanks or rail cars and pumped into the relocatable storagevessel(s).

The acrylonitrile may be removed from the relocatable storage vesselthrough a bottom valve by means of gravity or it may be pumped, forexample from the upper side using a suitable pump.

Biocatalysts

As biocatalyst for performing step [0], nitrile hydratase enzymes can beused, which are capable of catalyzing the hydrolysis of acrylonitrile toacrylamide. Typically, nitrile hydratase enzymes can be produced by avariety of microorganisms, for instance microorganisms of the genusBacillus, Bacteridium, Micrococcus, Brevibacterium, Corynebacterium,Pseudomonas, Acinetobacter, Xanthobacter, Streptomyces, Rhizobium,Klebsiella, Enterobacter, Escherichia Coli, Erwinia, Aeromonas,Citrobacter, Achromobacter, Agrobacterium, Pseudonocardia andRhodococcus. WO 2005/054456 discloses the synthesis of nitrile hydratasewithin microorganisms and therein it is described that various strainsof Rhodococcus rhodochrous species have been found to very effectivelyproduce nitrile hydratase enzymes, in particular Rhodococcus rhodochrousNCIMB 41164. Such microorganisms, suitable as biocatalyst for theenzymatic conversion of acrylonitrile to acrylamide, which are known fora person skilled in the art, are able to be applied in a relocatablebioconversion unit according to the present invention. Additionally, thespecific methods of culturing (or cultivation, or fermentation) and/orstoring the microorganism as well as the respective sequences ofpolynucleotides which are encoding the enzyme, particularly the nitrilehydratase, are known in the art, e.g. WO 2005/054456, WO 2016/050816,and are applicable in context of the present invention. Within thepresent invention nitrile hydratase and amidase producing microorganismsmay be used for converting a nitrile compound into the correspondingamide compound as it is described for example in WO 2016/050816.

The terms “nitrile hydratase (NHase) producing microorganism” or“microorganism” or “biocatalysts” or the like, have the meaning to beable to produce (i.e. they encode and express) the enzyme nitrilehydratase (also referred to as, e.g., NHase) either per se (naturally)or they have been genetically modified respectively. Microorganismswhich have been “genetically modified” means that these microorganismshave been manipulated such that they have acquired the capability toexpress the required enzyme NHase, e.g. by way of incorporation of anaturally and/or modified nitrile hydratase gene or gene cluster or thelike. Produced products of the microorganisms that can be used in thecontext of the present invention are also contemplated, e.g. suspensionsobtained by partial or complete cell disruption of the microorganisms.

The terms “nitrile hydratase (NHase) producing microorganism” or“microorganism” or “biocatalysts” or the like, include the cells and/orthe processed product thereof as such, and/or suspensions containingsuch microorganisms and/or processed products. It is also envisaged thatthe microorganisms and/or processed products thereof are further treatedbefore they are employed in the embodiments of the present invention.“Further treated” thereby includes for example washing steps and/orsteps to concentrate the microorganism etc. It is also envisaged thatthe microorganisms that are employed in the embodiments of the presentinvention have been pre-treated by a for example drying step. Also knownmethods for cultivating of the microorganisms and how to optimize thecultivation conditions via for example addition of urea or cobalt aredescribed in WO 2005/054456 and are compassed by the embodiments of thepresent invention. Advantageously, the microorganism can be grown in amedium containing acetonitrile or acrylonitrile as an inducer of thenitrile hydratase.

Preferably, the biocatalyst for converting acrylonitrile to acrylamidemay be obtained from culturing the microorganism in a suitable growthmedium. The growth medium, also called fermentation (culture) medium,fermentation broth, fermentation mixture, or the like, may comprisetypical components like sugars, polysaccharides, which are for exampledescribed in WO 2005/054489 and which are suitable to be used for theculturing the microorganism of the present inventions to obtain thebiocatalyst. For storage of the microorganism, the fermentation brothpreferably is removed in order to prevent putrefaction, which couldresult in a reduction of nitrile hydratase activity. The methods ofstorage described in WO 2005/054489 may be applied according to thepresent invention ensuring sufficient biocatalyst stability duringstorage. Preferably, the storage does not influence biocatalyticactivity or does not lead to a reduction in biocatalytic activity. Thebiocatalyst may be stored in presence of the fermentations brothcomponents. Preferred in the sense of the present invention is that thebiocatalyst may be stored in form of a frozen suspension and may bethawed before use. Further, the biocatalyst may be stored in dried formusing freeze-drying, spray drying, heat drying, vacuum drying, fluidizedbed drying and/or spray granulation, wherein spray drying and freezedrying are preferred.

Biocatalyst Make-Up

The biocatalysts that are used according to the present invention in themodular, relocatable plant can for example be cultured under anyconditions suitable for the purpose in accordance with any of the knownmethods, for instance as described in the mentioned prior art of thisspecification. The biocatalyst may be used as a whole cell catalyst forthe generation of amide from nitrile. The biocatalyst may be (partly)immobilized for instance entrapped in a gel or it may be used forexample as a free cell suspension. For immobilization well knownstandard methods can be applied like for example entrapment crosslinkage such as glutaraldehyde-polyethyleneimine (GA-PEI) crosslinking,cross linking to a matrix and/or carrier binding etc., includingvariations and/or combinations of the aforementioned methods.Alternatively, the nitrile hydratase enzyme may be extracted and forinstance may be used directly in the process for preparing the amide.When using inactivated or partly inactivated cells, such cells may beinactivated by thermal or chemical treatment.

In a preferred embodiment, the microorganisms are whole cells. The wholecells may be pre-treated by a drying step. Suitable drying methodsand/or drying conditions are disclosed e.g. in WO 2016/050816 and WO2016/050861 and the know art can be applied in the context of thepresent invention for the use in a relocatable bioconversion unit.

The microorganisms that are employed in the context of the presentinvention are in a preferred embodiment used in an aqueous suspensionand in a more preferred embodiment are free whole cells in an aqueoussuspension. The term “aqueous suspension” thereby includes all kinds ofliquids, such as buffers or culture medium that are suitable to keepmicroorganisms in suspension. Such liquids are well-known to the skilledperson and include for example storage buffers at suitable pH such asstorage buffers which are used to deposit microorganisms, TRIS-basedbuffers, saline based buffers, water in all quality grades such asdistilled water, pure water, tap water, or sea water, culture medium,growing medium, nutrient solutions, or fermentation broths, for examplethe fermentation broth that was used to culture the microorganisms.During storage for example the aqueous suspension is frozen and thawedbefore use, in particular without loss in activity.

The biocatalyst may be provided as powder or as aqueous suspension. Ifprovided as powder it is frequently advisable to prepare an aqueoussuspension before adding the catalyst into the bioconversion unit. In anembodiment, the biocatalyst suspension may be conducted by suspendingthe biocatalyst powder in water in a vessel comprising at least a mixingdevice, for example a stirrer, one or more inlets for water, thebiocatalyst and optionally further additives and one outlet for thebiocatalyst suspension. The volume of the vessel may be for example from0.1 m³ to 1 m³. The concentration of the biocatalyst in the aqueousbiocatalyst suspension may be for example from 1% to 30% by wt., forexample from 10 to 20% by wt. relating to the total of all components ofthe aqueous suspension.

A biocatalyst suspension may be added directly to the bioconversionunit. In another embodiment a concentrated suspension may be dilutedbefore adding it to the bioconversion unit.

Bioconversion

The hydrolysis of acrylonitrile to acryl amide by means of a biocatalystis performed in a suitable relocatable bioconversion unit.

Particularly, the bioconversion is performed by contacting a mixturecomprising water and acrylonitrile with the biocatalyst in therelocatable bioconversion unit. The term “contacting” is notspecifically limited and includes for example bringing into contactwith, admixing, stirring, shaking, pouring into, flowing into, orincorporating into. It is thus only decisive that the mentionedingredients come into contact with each other no matter how that contactis achieved.

Therefore, in one embodiment of the present invention step [0] comprisesthe following steps:

(a) Adding the following components (i) to (iii) to a bioconversion unitto obtain a composition for bioconversion:

-   -   (i) a biocatalyst capable of converting acrylonitrile to        acrylamide;    -   (ii) acrylonitrile;    -   (iii) aqueous medium; and

(b) performing a bioconversion on the composition obtained in step (a).

The bioconversion can for example be conducted under any conditionssuitable for the purpose in accordance with any of the known methods,for instance as described in the mentioned prior art of thisspecification like e.g. WO 2016/050817, WO 2016/050819, WO 2017/055518.

The conversion of acylonitrile to the acrylamide may be carried out byany of a batch process and a continuous process, and the conversion maybe carried out by selecting its reaction system from reaction systemssuch as suspended bed, a fixed bed, a fluidized bed and the like or bycombining different reaction systems according to the form of thecatalyst. Particularly, the method of the present invention may becarried out using a semi-batch process. In particular, the term“semi-batch process” as used herein may comprise that an aqueousacrylamide solution is produced in a discontinuous manner.

According to a non-limiting example for carrying out such a semi-batchprocess water, a certain amount of acrylonitrile and the biocatalyst areplaced in the bioconversion unit. Further acrylonitrile is then addedduring the bioconversion until a desired content of acrylamide of thecomposition is reached. After such desired content of acrylamide isreached, the obtained composition is for example partly or entirelyrecovered from the reactor, before new reactants are placed therein. Inparticular, in any one of the methods of the present invention theacrylonitrile may be fed such that the content of acrylonitrile duringstep (b) is maintained substantially constant at a predetermined value.In general, in any one of the methods of the present invention theacrylonitrile content and/or the acrylamide content during step (b) maybe monitored. Methods of monitoring the acrylonitrile contents are notlimited and include Fourier Transform Infrared Spectroscopy (FTIR). Inanother embodiment, the heat-balance of the reaction may be used formonitoring the process. This means that monitoring via heat-balancemethod takes place by measuring the heat energy of the system duringbioconversion and by calculating the loss of heat energy during thereaction in order to monitor the process.

Although the conversion of acrylonitrile to the acrylamide maypreferably be carried out at atmospheric pressure, it may be carried outunder pressure in order to increase solubility of acrylonitrile in theaqueous medium. Because biocatalysts are temperature sensitive and thehydrolysis is an exothermic reaction temperature control is important.The reaction temperature is not specifically restricted provided that itis not lower than the ice point of the aqueous medium. However, it isdesirable to carry out the conversion at a temperature of usually 0 to50° C., preferably 10 to 40° C., more preferably 15 to 30° C. Furthersuitable condition for the bioconversion according to the presentinvention are for example described in WO 2017/055518 and are preferablyapplicable for the method in a relocatable bioconversion unit.

Although the amount of biocatalyst may vary depending on the type ofbiocatalyst to be used, it is preferred that the activity of thebiocatalyst, which is introduced to the reactor, preferably therelocatable bioconversion unit, is in the range of about 5 to 500 U permg of dried cells of microorganism. Methods for determining the abilityof a given biocatalyst (e.g. microorganism or enzyme) for catalyzing theconversion of acrylonitrile to acrylamide are known in the art. As anexample, in context with the present invention, activity of a givenbiocatalyst to act as a nitrile hydratase in the sense of the presentinvention may be determined as follows: First reacting 100 μl of a cellsuspension, cell lysate, dissolved enzyme powder or any otherpreparation containing the supposed nitrile hydratase with 875 μl of a50 mM potassium phosphate buffer and 25 μl of acrylonitrile at 25° C. onan Eppendorf tube shaker at 1,000 rpm for 10 minutes.

After 10 minutes of reaction time, samples may be drawn and immediatelyquenched by adding the same volume of 1.4% hydrochloric acid. Aftermixing of the sample, cells may be removed by centrifugation for 1minute at 10,000 rpm and the amount of acrylamide formed is determinedby analyzing the clear supernatant by HPLC. For affirmation of an enzymeto be a nitrile hydratase in context with the present invention, theconcentration of acrylamide shall particularly be between 0.25 and 1.25mmol/l—if necessary, the sample has to be diluted accordingly and theconversion has to be repeated. The enzyme activity may then be deducedfrom the concentration of acrylamide by dividing the acrylamideconcentration derived from HPLC analysis by the reaction time, which hasbeen 10 minutes and by multiplying this value with the dilution factorbetween HPLC sample and original sample. Activities >5 U/mg dry cellweight, preferably >25 U/mg dry cell weight, more preferably >50 U/mgdry cell weight, most preferably >100 U/mg dry cell weight indicate thepresence of a functionally expressed nitrile hydratase and areconsidered as nitrile hydratase in context with the present invention.

It is preferred, that the concentration of acrylonitrile during thebioconversion should not exceed 6% by wt. and may for example be in therange from 0.1% by wt. to 6% by wt., preferably from 0.2% by wt. to 5%by wt., more preferably from 0.3% by wt. to 4% by wt., even morepreferably from 0.5% by wt. to 3% by wt., still more preferably from0.8% by wt. to 2% by wt. and most preferably from 1% by wt. to 1.5% bywt., relating to the total of all components of the aqueous mixture. Itis possible that the concentration may vary over time during thebioconversion reaction. In order to obtain more concentrated solutionsof acrylamide the total amount of acrylonitrile should not be added allat once but it should be added stepwise or even continuously keeping theabovementioned concentration limits in mind. The disclosure of WO2016/050818 teaches a method of additional dosing of acrylonitrile,which is suitable to be used and applied in the present invention.

The concentration of acrylamide in the obtained solution is in the rangefrom 10% to 80%, preferably in the range from 20% to 70%, morepreferably in the range from 30% to 65%, even more preferably in therange from 40% to 60%, most preferably in the range from 45% to 55% byweight of acrylamide monomers. The reaction should be carried out insuch a manner that the final concentration of acrylonitrile in the finalacrylamide solution obtained does not exceed 0.1% by weight relating tothe total of all components of the aqueous solution. Typical reactiontimes may be from 2 to 20 h, in particular 4 h to 12 h, for example 6 hto 10 h. After completion of the addition of acrylonitrile, the reactorcontents is allowed to further circulate for some time to complete thereaction, for example for 1 hour to 3 hours. The remaining contents ofacrylonitrile should preferably be less than 100 ppm ACN.

Suitable reactors for performing the bioconversion are known to theskilled artisan. Examples comprise vessels of any shape, for examplecylindrical or spherical vessels, or tube reactors. In one embodiment,the continuous tank reactor as disclosed in WO 2016/006556 A1 may beused for bioconversion.

In one embodiment of the invention, the relocatable bioconversion unitis similar to the relocatable storage unit for acrylonitrile asdescribed above. Using largely the same equipment for storingacrylonitrile or other monomers and the bioconversion step contributesto an economic process for manufacturing aqueous acrylamide solutions.

The relocatable bioconversion unit comprises a reaction vessel. Thevolume of the reaction vessel is not specifically limited and may rangefrom 10 m³ to 150 m³, for example it may be about 20 m³ to 50 m³.Preferably, the reaction vessel should be double walled and should behorizontal. Such a construction avoids installing a pit for thecollection of any leakage thereby ensuring an easier and quickerrelocation of the reaction unit.

The bioconversion unit furthermore comprises means for mixing thereaction mixture and means for controlling the temperature of thecontents of the vessel. The hydrolysis of acrylonitrile to acrylamide isan exothermal reaction and therefore heat generated in course of thereaction should be removed in order to maintain an optimum temperaturefor bioconversion.

The bioconversion unit furthermore usually comprises means formeasurement and control, for example means for controlling thetemperature or for controlling the pressure in the vessel.

For temperature control, the preferred bioconversion unit comprises anexternal temperature control cycle comprising a pump which pumps theaqueous reactor contents from the storage vessel through a heatexchanger and back into the storage vessel, preferably via an injectionnozzle.

In one embodiment, a separate, relocatable temperature control unit isused comprising pump and heat exchanger and which is connected with thebioconversion unit by pipes or flexible tubes. In a preferredembodiment, the temperature control cycle is integrated into therelocatable bioconversion unit. It may—for example—be located at one endof the unit besides the reaction vessel.

The reaction vessel may furthermore comprise means for mixing theaqueous reaction mixture, for example a stirrer.

Surprisingly, it has been found, that the external temperature controlcycle described above may also be used as means for mixing. The streamof the aqueous reaction mixture which passes through the temperaturecontrol cycle and which is injected back into the reaction vessel causesa circulation of the aqueous reaction mixture within the reaction vesselwhich is sufficient to mix the aqueous reaction mixture.

Preferably, no stirrer is used for the mobile bioconversion unit. Astirrer is an additional mechanical device, which increases thetechnical complexity. When using the external temperature control cyclefor mixing instead of a stirrer, the technical complexity can be reducedwhile still sufficient mixing during bioconversion can be ensured.Advantageously, without a stirrer a transportation step is easier, sinceno stirrer as additional technical component has to be removed beforetransportation. Further, a bioconversion unit without a stirrer offersmore flexibility in form, shape, mechanical stability requirements andsize for the bioconversion unit. In particular, a horizontal set-up forthe relocatable bioconversion unit can be realized easier without astirrer and with mixing just via the external temperature control cycle.

Adding acrylonitrile to the contents of the bioconversion unit may beperformed in various ways. It may be added into the reaction vessel orit may be added into the temperature control cycle, for example afterthe pump and before the heat exchanger or after the heat exchanger.Injecting acrylonitrile into the temperature control cycle ensures goodmixing of the reaction mixture with freshly added acrylonitrile.Preferably, acrylonitrile is added between pump and heat exchanger.

FIG. 3 schematically represents an embodiment of the relocatablebioconversion unit with an integrated temperature control cycle. Thebioconversion unit comprises a frame (10), a double-walled reactionvessel mounted into the frame comprising an outer wall (11) and an innerwall (12). Preferred volumes of the reaction vessel have already beenmentioned. In other embodiments, the reaction vessel is self-supportingand there is no frame (10). The reaction vessel is filled with thereaction mixture. The bioconversion unit furthermore comprises anexternal temperature control cycle comprising at least a pump (13) and atemperature control unit (14). The reaction mixture is circulated bymeans of a pump (13) from the reaction vessel to the temperature controlunit (14) and is injected back into the storage vessel, preferably viaan injection nozzle (16). In the depicted embodiment, acrylonitrile isinjected into the temperature control cycle thereby ensuring good mixing(15). It may be added before or after the temperature control unit. FIG.3 shows an embodiment in which acrylonitrile is added into thetemperature control cycle between the pump and the heat exchanger. Thestream of reaction mixture injected back into the reaction vessel causesa circulation of the reaction mixture in the reaction vessel whichensures sufficient mixing of the contents of the reaction mixture.

The amount of reaction mixture cycled per hour through the temperaturecontrol cycle is chosen such that sufficient mixing to the contents ofthe reactor as well as sufficient temperature control is achieved. Inone embodiment, the amount of reaction mixture cycled per hour throughthe temperature control cycle may be from 100% to 1000% of the totalvolume of the reaction mixture in the bioconversion unit, in particularfrom 200% to 1000% and for example from 500% to 800%.

Off-gases of the bioconversion unit may comprise acrylonitrile, acrylicacid and acrylamide. If necessary, according to the applicable rulessuch off-gases may be treated in a manner known in the art. For example,it may be possible to combust the off-gases.

In one embodiment, all off-gases containing acrylonitrile, acrylic acidand acrylamide may be washed in a scrubber. The scrubber vessel may havea volume of 1 m³ to 100 m³, preferably a volume of 5 m³ to 100 m³, morepreferably a volume of 10 m³ to 100 m³. It may be for example an ISOtank or relocatable storage vessel, preferably a double walled vessel.The scrubber water may preferably be collected in a tank and it may bere-used in the next bio-conversion batch.

Biomass Removal

After bioconversion, the reaction vessel comprises an aqueous solutionof acrylamide, which still comprises the biocatalyst suspended therein.

The biocatalyst preferably becomes removed completely, essentiallycompletely, or partially before polymerization, however, removing thebiocatalyst may not be absolutely necessary in every case. Whether it isnecessary to remove the biocatalyst substantially depends on twofactors, namely whether remaining biocatalyst negatively affectspolymerization and/or the properties of the polyacrylamide obtainedand/or the biocatalyst negatively affects the application of theobtained polyacrylamide solution. In one embodiment, at least 75%,preferably at least 90% by weight of the biomass—relating to the totalof the biomass present—should be removed.

The method for removing the biocatalyst is not specifically limited.Separation of the biocatalyst may take place by for example filtrationor centrifugation. In other embodiments, active carbon may be used forseparation purpose.

Procedurally, for removing the biocatalyst there are several options.

In one embodiment, the aqueous acrylamide solution comprising thebiocatalyst is removed from the bioconversion unit, passed through aunit for removing the biocatalyst, and thereafter the aqueous acrylamidesolution is filled into a suitable storage unit for acrylamide,preferably a relocatable storage unit for acrylamide as described above.

In another embodiment, the aqueous acrylamide solution comprising thebiocatalyst is removed from the bioconversion unit, passed through aunit for removing the biocatalyst and thereafter the aqueous acrylamidesolution is filled directly into the monomer make-up unit, i.e. withoutintermediate storing in an acrylamide storage unit.

In another embodiment, the aqueous acrylamide solution comprising thebiocatalyst is removed from the bioconversion unit and is filleddirectly, i.e. without removing the biocatalyst, into the monomermake-up unit. In said embodiment, the biocatalyst is still present incourse of monomer make-up and is removed after preparing the aqueousmonomer solution (step [1]) as described below.

In another embodiment, the aqueous acrylamide solution comprising thebiocatalyst is removed from the bioconversion unit, passed through aunit for removing the biocatalyst and thereafter filled back into thebioconversion unit. In order to ensure complete discharge of thebioconversion unit before re-filling it with the acrylamide solution,the unit for removing the biocatalyst should comprise a buffer vesselhaving a volume sufficient for absorbing the contents of thebioconversion unit.

The above-mentioned methods for biocatalyst removal are for exampleapplicable for partwise and/or complete removal of the biocatalyst.Further, it is preferred, that the completely or partly removedbiocatalyst may be reused for a subsequent bioconversion reaction.

Provision of Acrylic Acid

In the context of the present invention, acrylic acid or salts thereofmay be used as comonomer besides acrylamide. Basically, any kind ofacrylic acid may be used for the process according to the presentinvention, for example acrylic acid obtained by catalytic oxidation ofpropene. In one embodiment of the invention ammonium acrylate availableby enzymatic hydrolysis of acrylonitrile may be used for carrying outthe process according of the present invention (hereinafter also “bioacrylate”).

In a preferred embodiment of the present invention the manufacture ofammonium acrylate by enzymatic hydrolysis of acrylonitrile is alsoperformed at the site of the modular plant in a modular unit. Suitableenzymes have been disclosed in WO 97/21827 A1 and the literature citedtherein, and the publication describes also suitable conditions forcarrying out the reaction. The manufacture of bio-acrylate may becarried out using stirred tank reactors or loop reactors, and inparticular, the relocatable bioconversion unit described above may alsobe used.

Manufacturing bio-acrylate on-site also saves transport costs. Althoughacrylic acid may be provided to the site of the modular plant as purecompound, its molecular weight is −36% higher than that ofacrylonitrile.

Step [1]—Preparation of an Aqueous Monomer Solution

In course of step [1] an aqueous monomer solution comprising at leastwater, acrylamide and optionally further water-soluble,monoethylenically unsaturated monomers is prepared in a relocatablemonomer make-up unit.

Monomer Storage

Basically, it is possible to run step [1] as just-in-time-process, i.e.providing the monomers to the relocatable plant when monomers are neededand directly withdrawing the monomers from the transport vessels.However, in order to ensure an uninterrupted operation is preferred tohold available at least some storage capacity for the monomers at thelocation of the modular, relocatable plant.

Depending on the chemical nature, any water-soluble, monoethylenicallyunsaturated monomers to be used may be provided as pure monomers or asaqueous solutions to the plant. It is also possible to provide a mixtureof two or more water-soluble, monoethylenically unsaturated monomers, inaqueous solution or as pure monomers, to the modular plant. Acrylamideand other water-soluble, monoethylenically unsaturated monomers such asacrylic acid, ATBS, or DM3AQ, or mixtures thereof, preferably may bestored in relocatable storage units. Details of such relocatable storageunits for monomers have already been outlined above for acrylonitrileand we refer to the description above.

The monomers may be provided to the plant by road tankers, ISOtanks, orrail cars and pumped into the relocatable storage unit(s).

In one embodiment, a relocatable storage unit with integratedtemperature control cycle as depicted in FIG. 1 as shown above may beused for storing the monomers.

In another embodiment, a relocatable storage unit with a separate,external temperature control cycle as depicted in FIG. 2 as shown abovemay be used for storing the monomers.

As a rule, the temperature of the monoethylenically unsaturated monomerssuch as acrylamide, acrylic acid, ATBS or DM3AQ should not exceed 25° C.to 30° C.

Pure associative monomers as described above may be waxy solids and maybe stored at room temperature. They may be stored as aqueous solutions,for example as aqueous solutions comprising 25% by weight of theassociative monomer. Because the amounts of associative monomers aresignificantly smaller than the amounts of other monoethylenicallyunsaturated monomers smaller relocatable storage units than thatdescribed above may be used.

Acidic monomers such as acrylic acid or ATBS are often partially orcompletely neutralized for polymerization using suitable bases.

Bases, such as aqueous solutions of NaOH may also be stored in storagevessels as described above. A cooling cycle is not necessary. To thecontrary, depending on the climatic conditions, a heating such as aheating element in the vessel may be necessary because concentrated NaOHfreezes at about +15° C.

Monomer Make-up

The aqueous monomer solution for polymerization to be prepared in courseof step [1] in the relocatable monomer make-up unit comprises water and5% to 45% by weight, preferably 15% to 45% by weight of water-soluble,monoethylenically unsaturated monomers, relating to the total of allcomponents of the aqueous monomer solution. The water-soluble,monoethylenically unsaturated monomers comprise at least acrylamide,preferably bio acrylamide which preferably is manufactured in step [0]also at the location of the modular, relocatable plant. The monomerconcentration may be selected by the skilled artisan according tohis/her needs. Details about adequately selecting the monomerconcentration will be provided below.

In one embodiment of the invention, the monomer concentration is from 8%by weight to 24.9% by weight, preferably from 15% by weight to 24.9% byweight, for example from 20 to 24.9% by weight, relating to the total ofall components of the aqueous monomer solution.

For preparing the aqueous monomer solution, the water-soluble,monoethylenically unsaturated monomers to be used are mixed with eachother. All monomers and optionally additives may be mixed with eachother in a single step but it may also be possible to mix some monomersand add further monomers in a second step. Also, water for adjusting theconcentration of the monomers may be added. Water eventually used forrinsing lines in course of transferring the monomer solution into thepolymerization unit, needs to be taken into consideration when adjustingthe concentration.

Further additives and auxiliaries may be added to the aqueous monomersolution.

Examples of such further additives and auxiliaries comprise bases oracids for adjusting the pH value. In certain embodiments of theinvention, the pH-value of the aqueous solution is adjusted to valuesfrom pH 5 to pH 7, for example pH 6 to pH 7.

Examples of further additives and auxiliaries comprise complexingagents, defoamers surfactants, or stabilizers.

In one embodiment, the aqueous monomer solution comprises at least onestabilizer for the prevention of polymer degradation. The stabilizersfor the prevention of polymer degradation are what are called“free-radical scavengers”, i.e. compounds which can react with freeradicals (for example free radicals formed by heat, light, redoxprocesses), such that said radicals can no longer attack and hencedegrade the polymer. Using such kind of stabilizers for thestabilization of aqueous solutions of polyacrylamides basically is knownin the art, as disclosed for example in WO 2015/158517 A1, WO2016/131940 A1, or WO 2016/131941 A1.

The stabilizers may be selected from the group of non-polymerizablestabilizers and polymerizable stabilizers. Polymerizable stabilizerscomprise a monoethylenically unsaturated group and become incorporatedinto the polymer chain in course of polymerization. Non-polymerizablestabilizers don't comprise such monoethylenically unsaturated groups andare not incorporated into the polymer chain.

In one embodiment of the invention, stabilizers are non-polymerizablestabilizers selected from the group of sulfur compounds, stericallyhindered amines, N-oxides, nitroso compounds, aromatic hydroxylcompounds or ketones.

Examples of sulfur compounds include thiourea, substituted thioureassuch as N,N′-dimethylthiourea, N,N′-diethylthiourea,N,N′-diphenylthiourea, thiocyanates, for example ammonium thiocyanate orpotassium thiocyanate, tetramethylthiuram disulfide, and mercaptans suchas 2-mercaptobenzothiazole or 2-mercaptobenzimidazole or salts thereof,for example the sodium salts, sodium dimethyldithiocarbamate,2,2′-dithiobis(benzothiazole), 4,4′-thiobis(6-t-butyl-m-cresol).

Further examples include dicyandiamide, guanidine, cyanamide,paramethoxyphenol, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole,8-hydroxyquinoline, 2,5-di(t-amyl)-hydroquinone,5-hydroxy-1,4-naphthoquinone, 2,5-di(t-amyl)hydroquinone, dimedone,propyl 3,4,5-trihydroxybenzoate, ammonium N-nitrosophenylhydroxylamine,4-hydroxy-2,2,6,6-tetramethyoxylpiperidine,(N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine and1,2,2,6,6-pentamethyl-4-piperidinol.

Preference is given to sterically hindered amines such as1,2,2,6,6-pentamethyl-4-piperidinol and sulfur compounds, preferablymercapto compounds, especially 2-mercaptobenzothiazole or2-mercaptobenzimidazole or the respective salts thereof, for example thesodium salts, and particular preference is given to2-mercaptobenzothiazole or salts thereof, for example the sodium salts.

The amount of such non-polymerizable stabilizers—if present—may be from0.1% to 2.0% by weight, relating to the total of all monomers in theaqueous monomer solution, preferably from 0.15% to 1.0% by weight andmore preferably from 0.2% to 0.75% by weight.

In another embodiment of the invention, the stabilizers arepolymerizable stabilizers substituted by a monoethylenically unsaturatedgroup. Examples of stabilizers comprising monoethylenically unsaturatedgroups comprise (meth)acrylic acid esters of1,2,2,6,-pentamethyl-4-piperidinol or other monoethylenicallyunsaturated groups comprising 1,2,2,6,6-pentamethyl-piperidin-4-ylgroups. Specific examples of suitable polymerizable stabilizers aredisclosed in WO 2015/024865 A1, page 22, lines 9 to 19. In oneembodiment of the invention, the stabilizer is a (meth)acrylic acidester of 1,2,2,6,6-pentamethyl-4-piperidinol.

The amount of polymerizable stabilizers—if present—may be from 0.01 to2% by weight, based on the sum total of all the monomers in the aqueousmonomer solution, preferably from 0.02% to 1% by weight, more preferablyfrom 0.05% to 0.5% by weight.

In one embodiment, the aqueous monomer solution comprises at least onenon-polymerizable surfactant. Adding such surfactants in particular isadvisable when associative monomers are used. For such kind ofpolyacrylamides the surfactants lead to a distinct improvement of theproduct properties. Examples of suitable surfactants including preferredamounts have been disclosed in WO 2015/158517 A1, page 19, line, 23 topage 20, line 27. If present, such non-polymerizable surfactant may beused in an amount of 0.1 to 5% by weight, for example 0.5 to 3% byweight based on the amount of all the monomers used.

The relocatable monomer make-up unit may be any kind of equipment forthe mixing monomers provided that it is relocatable, for example astirred, relocatable vessel.

In one embodiment, a relocatable monomer make-up unit is similar to therelocatable bioconversion unit as described above. Using largely thesame equipment for storing acrylonitrile or other monomers, thebioconversion step and for monomer make-up contributes to an economicprocess for manufacturing aqueous acrylamide solutions.

The relocatable monomer make-up unit comprises a monomer make-up vesselin which the monomers, water and optionally further components aremixed.

The volume of the monomer make-up vessel is not specifically limited andmay range from 10 m³ to 150 m³, for example it may be about 20 to 90 m³.Preferably, the monomer make-up vessel should be double walled andshould be horizontal. Such a construction avoids installing a pit forthe collection of any leakage thereby ensuring an easier and quickerrelocation of the reaction unit.

The relocatable monomer make-up unit furthermore comprises means forcontrolling the temperature of the aqueous monomer solution. Usually,the temperature of the aqueous monomer solution should be not more than5° C., for example from −5° C. to +5° C. The monomer make-up unitfurthermore comprises means for measurement and control.

For temperature control, the relocatable monomer make-up unit comprisesan external temperature control cycle comprising a pump which pumps theaqueous reactor contents from the storage vessel through a heatexchanger and back into the storage vessel, preferably via an injectionnozzle.

The temperature control cycle may be a separate, relocatable temperaturecontrol unit comprising pump and heat exchanger which is connected withthe monomer make-up vessel by pipes or flexible tubes. In anotherembodiment, the temperature control cycle may be integrated intorelocatable monomer make-up unit. It may—for example—be located at oneend of the unit besides the monomer make-up vessel.

The monomer make-up vessel may be equipped with a stirrer for mixing thecomponents of the aqueous monomer solution with each other.

However, in the same manner as with the bioreactor, the externaltemperature control cycle may be used as means for mixing. The stream ofthe aqueous monomer mixture which passes through the temperature controlcycle and which is injected back into the monomer make-up vessel causesa circulation of the aqueous reaction mixture within the reaction vesselwhich is sufficient to mix the aqueous reaction mixture.

FIG. 4 represents a schematically one embodiment of the relocatablemonomer make-up unit. The monomer make-up unit comprises a frame (20), adouble-walled monomer make-up vessel mounted into the frame comprisingan outer wall (21) and an inner wall (22). In another embodiment, themonomer make-up vessel is self-supporting and a frame is not necessary.The monomer make-up vessel is filled with the monomer mixture. Themonomer make-up unit furthermore comprises an external temperaturecontrol cycle comprising at least a pump (23) and a temperature controlunit (24). The monomer mixture is circulated by means of a pump (23)from the storage vessel to the temperature control unit (24) and isinjected back into the storage vessel, preferably via an injectionnozzle (25). The monomers may be added directly into the storage vesselor into the temperature control cycle (26) as indicated in FIG. 4. Thestream of monomer mixture injected back into the monomer make-up vesselcauses a circulation of the monomer mixture in the storage vessel whichensures sufficient mixing of the contents of the monomer mixture.

In another embodiment, a separate temperature control cycle may be used.

The monomers to be mixed with each other and with water are preferablymixed in the monomer make-up vessel, however in another embodiment, itis possible to add the monomers into the temperature control cycle. Itis frequently advisable, to first add water to the monomer make-upvessel and then one or more further monomers and/or acids or basesand/or further additives. If acidic monomers such as acrylic acid areused, they should be neutralized before adding acrylamide. Forcopolymers comprising acrylic acid and acrylamide at first the necessaryamount of water may be added into the vessel, followed by NaOH,thereafter acrylic acid and thereafter acrylamide.

Further additives which optionally might be present such as complexingagents, defoamers surfactants, or stabilizers as mentioned above may bedissolved in aqueous solvents, preferably water in suitable dissolutionunits and the solutions also added into the monomer make-up vessel.

In another embodiment of the invention, the bioconversion unit may alsobe used for monomer make-up.

In a preferred embodiment, the aqueous acrylamide solution does nolonger comprise the biocatalyst. However, in another embodiment the acylamide solution still comprises the biomass. In said embodiment, thebiocatalyst may be removed after preparing the aqueous monomer solutionin the same manner as described above or it may not be removed. Criteriafor deciding in which cases it may not be necessary to remove thebiocatalyst have already been mentioned above.

After mixing the aqueous monomer solution it is transferred from therelocatable monomer make-up unit or any other unit serving as monomermake-up vessel such as the bioconversion unit to the polymerizationunit. Such connection for transferring the aqueous monomer solutionhereinafter also is referred to as “monomer feed line”.

In one embodiment, associative monomers may also be added into themonomer make-up vessel. However, in a preferred embodiment, aqueoussolutions of the associative monomers, in particular associativemonomers having the formula (III), (IV), or (V) may be metered into themonomer feed line.

In another embodiment of the invention, the relocatable polymerizationunit itself may be used for monomer make-up. As will be detailed below,the relocatable polymerization unit may be connected to a temperaturecontrol unit before polymerization, so that the monomer solution mayalso be cooled in the polymerization unit until directly before thestart of polymerization. As will be detailed also below, thepolymerization unit may comprise injection nozzles for nitrogen or otherinert gases in order to inert the contents of the polymerization unitand such injection of inert gases also efficiently mixes the contents ofpolymerization unit. Also, combinations are possible, for exampleproviding a monomer concentrate in a separate, relocatable monomermake-up unit and diluting the aqueous monomer solution in therelocatable polymerization unit with additional water. In anotherexample, acids or bases—if necessary—may be added not into a separatemonomer make-up unit but directly to the polymerization unit.

Step [2]—Polymerization

In course of step [2] the aqueous monomer solution prepared in step [1]is polymerized in the presence of suitable initiators for radicalpolymerization under adiabatic conditions thereby obtaining an aqueouspolyacrylamide gel.

Such a polymerization technique is also briefly denominated by theskilled artisan as “adiabatic gel polymerization”. Reactors foradiabatic gel polymerization are unstirred. Due to the relatively highmonomer concentration the aqueous monomer solution used solidifies incourse of polymerization thereby yielding an aqueous polymer gel. Theterm “polymer gel” has been defined for instance by L. Z. Rogovina etal., Polymer Science, Ser. C, 2008, Vol. 50, No. 1, pp. 85-92.

“Adiabatic” is understood by the person skilled in the art to mean thatthere is no exchange of heat with the environment. This ideal isnaturally difficult to achieve in practical chemical engineering. In thecontext of this invention, “adiabatic” shall consequently be understoodto mean “essentially adiabatic”, meaning that the reactor is notsupplied with any heat from the outside during the polymerization, i.e.is not heated, and the reactor is not cooled during the polymerization.However, it will be clear to the person skilled in the artthat—according to the internal temperature of the reactor and theambient temperature—certain amounts of heat can be released or absorbedvia the reactor wall because of temperature gradients, but this effectnaturally plays an ever lesser role with increasing reactor size.

The polymerization of the aqueous monomer solution generatespolymerization heat. Due to the adiabatic reaction conditions thetemperature of the polymerization mixture increases in course ofpolymerization.

The polymerization is performed in a relocatable polymerization unithaving a volume of 1 m³ to 100 m³, in particular 1 to 40 m², preferablyfrom 5 m³ to 40 m³, more preferably 5 to 30 m³ and more preferably 20 m³to 30 m³.

The transportable polymerization unit may be of cylindrical or conicalshape.

Preferably, the polymerization unit is cylindrical having a conicaltaper at the bottom and a bottom opening for removing the aqueous polyacrylamide gel. In one embodiment, there may be additionally acylindrical section between the lower end of the conical taper and thebottom opening. The inner wall of the transportable polymerization unitmay preferably be coated with an anti-adhesive coating. Basically,anti-adhesive coatings are known in the art. Examples comprisepolypropylene, polyethylene, epoxy resins and fluorine containingpolymers such as polytetrafluoroethylene or perfluoroalkoxy polymers.

One embodiment of a relocatable polymerization unit for use in thepresent invention is schematically shown in FIG. 5, hereinafter alsodenoted as polymerization unit P1. The relocatable polymerization unitP1 comprises a cylindrical upper part (30) and a conical part (31) atits lower end. At the lower end, there is a bottom opening (32) whichmay be opened and closed. After polymerization, the polyacrylamide gelformed is removed through the opening (32). It furthermore comprisesmeans (33) such as legs or similar elements allowing to deploy therelocatable polymerization unit in a vertical manner. The volume of thetransportable polymerization unit P1 described herein may be from 5 m³to 40 m³, preferably from 20 m³ to 30 m³.

The diameter (D) of the polymerization unit P1 in the cylindricalsection may in particular be from 1.5 to 2.5 m, preferably from 2 m to2.5 m and the length (L) of the cylindrical section may be from 4 to 6m, preferably 5 to 6 m. The conus angle α in the conical part (see alsoFIG. 4) may be from 15° to 90°, preferably from 20° to 40°. Besides theopening (32) the relocatable polymerization unit P1 comprises one ormore feeds for the aqueous monomer solution, initiator solutions, gasessuch as nitrogen or other additives. The inner wall of the transportablepolymerization unit P1 may be coated with an anti-adhesive coating. Thediameter of the bottom opening (32) may for example be from 0.2 to 0.8m, in particular from 0.4 to 0.7 m, preferably from 0.5 to 0.7 m.

The relocatable polymerization unit P1 is operated in a verticalposition as depicted in FIG. 5. For transport, it may preferably betilted to a horizontal position.

For polymerization, the aqueous monomer solution prepared in course ofstep [1] is filled into the relocatable polymerization unit, inparticular into the polymerization unit P1. For that purpose, therelocatable monomer make-up unit or any other unit serving as monomermake-up unit such as the bioconversion unit is connected with thepolymerization unit by a monomer feed line.

As already outlined above, in another embodiment the aqueous monomersolution may be prepared in the polymerization unit itself. In suchembodiment, the polymerization unit already is filled with an aqueousmonomer solution and it is no longer necessary to fill the monomersolution into the relocatable polymerization unit.

The polymerization is performed in the presence of suitable initiatorsfor radical polymerization. Suitable initiators for radicalpolymerization, in particular for adiabatic gel polymerization are knownto the skilled artisan.

In a preferred embodiment, redox initiators are used for initiating.Redox initiators can initiate a free-radical polymerization even attemperatures of less than +5° C. Examples of redox initiators are knownto the skilled artisan and include systems based on Fe²⁺/Fe³⁺—H₂O₂,Fe²⁺/Fe³⁺-alkyl hydroperoxides, alkyl hydroperoxides-sulfite, forexample t-butyl hydroperoxide-sodium sulfite, peroxides-thiosulfate oralkyl hydroperoxides-sulfinates, for example alkylhydroperoxides/hydroxymethane-sulfinates, for example t-butylhydroperoxide-sodium hydroxymethanesulfinate.

Furthermore, water-soluble azo initiators may be used. The azoinitiators are preferably fully water-soluble, but it is sufficient thatthey are soluble in the monomer solution in the desired amount.Preferably, azo initiators having a 10 h t_(1/2) in water of 40° C. to70° C. may be used. The 10-hour half-life temperature of azo initiatorsis a parameter known in the art. It describes the temperature at which,after 10 h in each case, half of the amount of initiator originallypresent has decomposed.

Examples of suitable azo initiators having a 10 h t_(1/2) temperaturebetween 40 and 70° C. include 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (10 h t_(1/2) (water): 44° C.),2,2′-azobis(2-methylpropionamidine) dihydrochloride (10 h t_(1/2)(water): 56° C.), 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidinehydrate (10 h t_(1/2) (water): 57° C.),2,2′-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride (10 h t_(1/2) (water): 60° C.),2,2′-azobis(1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride (10 ht_(1/2) (water): 67° C.) or azobis(isobutyronitrile) (10 h t_(1/2)(toluene): 67° C.).

In one embodiment of the invention a combination of at least one redoxinitiator and at least one azo initiator is used. The redox initiatorefficiently starts polymerization already at temperatures below +5° C.When the reaction mixture heats up, also the azo initiators decomposeand also start polymerization.

The initiators preferably are added as aqueous solutions to the aqueousmonomer solution. The initiator raw material may be stored in a coldstorage container. Dissolving the initiators in water may be performedusing suitable relocatable initiator make-up vessels. The initiatormake-up vessel may comprise a temperature control cycle. Instead of anown temperature control cycle, cold water, for example water having atemperature of less than +5° C. may be used for dissolving theinitiators. The initiator make-up vessels furthermore may comprise meansfor mixing such as a stirrer. However, mixing may also be conducted bybubbling an inert gas through the aqueous mixture thereby simultaneouslymixing and inerting the aqueous mixture. The solutions may be filteredbefore use.

Solutions of azo initiators may be added into the monomer feed linewhile the aqueous monomer solution is transferred from the relocatablemonomer make-up unit to the relocatable polymerization unit. In anotherembodiment solutions of azo initiators may already be added to themonomer make-up vessel, provided the monomer solution has already beencooled to temperatures below ambient temperature, preferably to lessthan +5° C. and the 10 h t_(1/2) temperature of the initiator is highenough so that the initiator doesn't decompose prematurely.

Solutions of redox initiators may be added into the monomer feed line orinto the relocatable polymerization unit.

Before polymerization oxygen from the reactor and the reaction mixtureto be polymerized needs to be removed. Deoxygenation is also known asinertization.

In one embodiment, inertization is performed in the relocatablepolymerization unit. For that purpose, inert gases such as nitrogen orargon are injected into the reactor filled with the monomer solution.Preferably, nozzles for injecting inert gases are located in the bottomof the polymerization unit. In the relocatable polymerization unit P1they may for example be located in the conical taper. The bubbles ofinert gases rising in the reactor remove oxygen and simultaneously mixthe contents of the reactor very efficiently. Initiator solutionsmetered into the reactor are mixed with the aqueous solution by means ofthe inert gas injection.

In another embodiment, inertization may be performed in the monomer feedline. Inert gases such as nitrogen or argon may be injected into thefeed line. In order to ensure effective mixing of the gas injected andthe aqueous gases injected it is frequently desirable that the monomerfeed line additionally comprises a static mixture. The gas injected intothe monomer feed line may be removed before entering into the reactor bymeans of a suitable degassing unit such as the degassing units describedin WO 2003/066190 A1 or in CN 202492486 U. In another embodiment, noseparate degassing unit is used, but the solution is degassed afterentering into the polymerization unit. In one embodiment, the monomersolution enters into the reactor by means of a spray nozzle for thepurpose of removing gas.

Of course, it is possible to combine the two embodiments for degassing,i.e. to purging the relocatable polymerization unit with inert gases anddegassing the monomer mixture.

The radical polymerization starts after adding the initiator solutions,preferably solutions of redox initiators, to the aqueous monomersolution thereby forming an aqueous polyacrylamide gel. Due to thepolymerization heat generated in course of polymerization and theadiabatic reaction conditions, the temperature in the polymerizationunit increases.

In the following, the temperature of the aqueous monomer solution beforethe onset of polymerization shall be denominated as T₁ and thetemperature of the aqueous polymer gel directly after polymerizationshall be denominated as T₂. It goes without saying that T₂>T₁.

Within the context of the present invention, the temperature T₁ shouldnot exceed 30° C., in particular T₁ should not exceed 25° C. Preferably,T₁ should not exceed 10° C., more preferably not +5° C. In oneembodiment, T₁ may be from −5° C. to +30° C., for example from −5° C. to+25° C., preferably from −5° C. to +5° C., and more preferably from −5°C. to +5° C. The temperature T₁ of the monomer solution may be adjustedas already disclosed above, i.e. already the monomer solution in themonomer make-up vessel may be cooled appropriately. Of course, also thetemperature control unit for adjusting T₁ may be located in the monomerfeed line, or the polymerization unit may be connected to a temperaturecontrol unit before polymerization, so that the monomer solution maystill be cooled in the polymerization unit until directly before thestart of polymerization.

As the polymerization is carried out under adiabatic conditions, thetemperature T₂ reached in course of polymerization is not influenced byexternal heating or cooling but only depends on the polymerizationparameters chosen. But suitable choice of the polymerization parameters,the skilled artisan can adjust T₂. Because the reaction is adiabatic,the temperature increase in course of polymerization basically dependson the heat of polymerization generated in course of polymerization, theheat capacity of contents of the polymerization unit and the temperatureT₁ of the monomer solution, i.e. the temperature before the onset ofpolymerization. Due to high water contents of the mixture forpolymerization the heat capacity of the mixture for polymerization isdominated by the heat capacity of water and it may of course bemeasured. The polymerization heat per mole (or per mass) for commonmonoethylenically unsaturated monomers is known in the art and maytherefore be gathered from the scientific literature. Of course, it mayalso be measured. So, it is possible for the skilled artisan tocalculate at least roughly the heat of polymerization for specificmonomer compositions and specific monomer concentrations. The higher theconcentration of the monoethylenically unsaturated monomers in theaqueous solution the more heat of polymerization is generated. T₂ may beroughly calculated from the parameter mentioned above by the formulaT₂=T₁+[(polymerization heat)/(heat capacity)]. The temperature T₂ shouldbe at least 45° C., preferably at least 50° C., for example from 50° C.to 100° C., for example from 55° C. to 95° C. In an embodiment of theinvention T₁ is from −15° C. to +5° C. and T₂ is from 50° C. to 95° C.

In one embodiment of the invention, T₂ does not exceed 70° C.,preferably it does not exceed 65° C. On the other hand, it shouldn't betoo low, in order to ensure an essentially complete polymerization. Incertain embodiments of the invention, T₂ should be from 45° C. to 70°C., in particular from 50° C. to 70° C., preferably from 50° C. for 65°C. For example, it may be from 55° C. to 65° C. In one embodiment, T₁ isfrom −15° C. to +5° C. and T₂ is from 50° C. to 70° C., preferably from50° C. for 65° C. and for example from 55° C. to 65° C.

Limiting T₂ to temperatures ≤70° C. may be achieved by the measuresmentioned above. In particular, it is advisable to choose aconcentration of monomers in the aqueous polymer solution of 5% byweight to 24.9% by weight relating to the total of all components of theaqueous solution, in particular 8% by wt. to 24.9% by weight and forexample 20% by weight to 24.9% by weight. In addition, T₁ may be −5° C.to +5° C.

The time of polymerization may be from 2 to 24 h, for example from 3 to6 h.

For lower concentrations, T₁ may also be chosen to be more than +5° C.For concentrations around 20% by weight, T₁ may be chosen to be around+10° C. to achieve a T₂ in the range from 50° C. to 65° C. Forconcentrations around 15% by weight, T₁ may be chosen to be around +25°C. to achieve a T₂ in the range from 50° C. to 65° C.

Step [3] Removal of the Aqueous Polyacrylamide Gel

In course of step [3], the aqueous polyacrylamide gel is removed fromthe relocatable polymerization unit. After removal from thepolymerization unit the aqueous polymer gel is further processed bycomminuting and dissolving the aqueous polyacrylamide gel in an aqueousfluid.

Basically, removing the aqueous polyacrylamide gel may be performed byany kind of technology. The details depend on the specific design of thepolymerization vessel and the connected downstream processing equipment.

Preferably, the aqueous polyacrylamide gel may be removed by applyingpressure onto the gel and pressing it through an opening in therelocatable polymerization unit. By the way of example, pressure may begenerated by mechanical means such as a piston, by means of gases suchas compressed air, nitrogen, argon or by means of aqueous fluids, inparticular water. Preferably, gases and/or aqueous fluids are used.

For removing the polyacrylamide gel from the preferred relocatablepolymerization unit P1, the relocatable polymerization unit P1 isoperated in vertical position. The aqueous polyacrylamide gel is removedthrough the opening (26) at the bottom which is opened for the purposeof removing by applying pressure onto the gel from the top side of thereactor. Pressure may be applied using gases and/or water. Examples ofgases comprise pressurized air, nitrogen or argon. Basically, any kindof gas may be used, provided it does not react with the polyacrylamidegel. In another embodiment, the relocatable polymerization unit maycomprise mechanical means, such as a piston for generating pressure. Thepressure to be applied for removing the gel may be selected by theskilled artisan. Factors relevant for the selection of the pressureinclude the viscosity of the polyacrylamide gel, the width of the bottomopening (26), the geometry of the polymerization unit or—if present—thekind of anti-adhesive layer. For example, pressures may range from110,000 Pa to 1,000,000 Pa, in particular 150,000 Pa to 750,000 Pa, forexample 200,000 Pa to 500,000 Pa (absolute pressures). Removing theaqueous polyacrylamide gel may be supported by a thin water-film at theinner walls of the reactor, in particular on the walls of the conicalpart of the reactor. Such a thin water-film may be generated byinjecting water or an aqueous fluid through fine holes in the wall ofthe reactor into the reactor, in particular holes in the conical part.Should some polymer gel remain in the polymerization unit, thepolymerization unit may be rinsed with water to remove the remainingamounts.

The bottom opening (26) of the polymerization unit P1 may be connectedwith a comminution unit—if present—or directly with a suitabledissolution unit, for instance with a stirred vessel. Said connectionmay simply be a pipe but it may also comprise means for transporting thegel such as for example screw conveyors or belt conveyors.

In other embodiments, the polyacrylamide gel may be conveyed by the gaspressure from the polymerization reactor into a pump. Such a pump may behelpful in achieving a constant feed rate and a constant pressure forthe consecutive step [4] of comminuting and dissolving thepolyacrylamide gel. Depending on the nature of the equipment used forstep [5] ensuring constant feed rate and a constant pressure may bedifficult to achieve by gas pressure alone. A pump may in particular behelpful, if it is the aim to convey the polyacrylamide gel through acomminution unit in course of step [4] causing a significant pressuredrop, such as for example conveying the polyacrylamide gel through ahole perforation plate and/or conveying the gel through a relativelylong pipe.

Suitable are all pumps capable of transporting the polyacrylamide gel,in particular positive displacement pumps such as a progressive cavitypump or a screw spindle pump.

Steps [4] and [5] Comminution and Dissolution of the AqueousPolyacrylamide Gel

In course of step [4] the aqueous polyacrylamide gel is comminuted andin course of step [5] dissolved in an aqueous liquid, thereby obtainingan aqueous polyacrylamide solution.

Comminuting the aqueous polyacrylamide gel before dissolution in anaqueous liquid is helpful, because smaller gel particles dissolve morequickly in the aqueous liquid than larger gel particles. It should bekept in mind that already removing the aqueous polyacyrylamide gel fromthe polymerization unit (i.e. step [3]) may cause some disintegration ofthe gel into smaller gel pieces.

Steps [4] and [5] may be separate steps to be conducted consecutively orthe steps may be combined with each other. In other embodiments, alreadysome of the polyacrylamide gel may be dissolved in course of step [4]but dissolution mostly takes place in a consecutive step [5]. As will bedetailed below, step [4] may comprise adding already some aqueousliquid, preferably water, to the aqueous polyacrylamide gel and acertain amount of the aqueous polyacrylamide gel might already dissolvein course of step [4], thereby yielding aqueous polyacrylamide gelpieces suspended in an aqueous polyacrylamide solution.

The aqueous liquid used for dissolving the aqueous polyacrylamide gelcomprises water. The term “water” includes any kind of water such asdesalinated water, fresh water or water comprising salts, such asbrines, sea water, formation water, produced water or mixtures thereof.Besides water, the aqueous liquid may comprise organic solvents misciblewith water, however the amount of water relating to the total of allsolvent should be at least 70% by weight, preferably at least 90% byweight, more preferably at least 95% by weight. In one preferredembodiment, the aqueous liquid comprises only water as solvent.Furthermore, the aqueous liquid may optionally also comprise additivessuch as for example surfactants, complexing agents, bases, acids of thelike. Kind and amount of such additives may be selected according to theintended use of the aqueous polyacrylamide solution. Of course,additives may also be added at a later stage, for example after completedissolution of the aqueous polyacrylamide gel.

The concentration of the aqueous polyacrylamide solution to be obtainedin course of step [5] may be selected by the skilled artisan accordingto the intended use of the solution. The term “aqueous solution” shallnot be limited to dilute aqueous solutions but shall also encompassconcentrates. It goes without saying, that the polyacrylamideconcentration of an aqueous solution obtained after carrying out step[5] necessarily is lower than the concentration of the aqueouspolyacrylamide gel before carrying out step [5]. More concentratedsolutions may require—depending on the viscosities of suchsolutions—pressure, for example pressure created by pumps for transportin pumps. The viscosities of polyacrylamide solutions depend as a matterof principle on various factors such as chemical composition, chemicalcomposition of the aqueous solvent, molecular weight, temperature, pHvalue or concentration.

In particular, the concentrations of the aqueous polyacrylamidesolutions may be up to 14.9% by weight, for example from 0.01 to 14.9%by weight, preferably from 0.01 to 7% by weight.

Typically, the concentration of the diluted aqueous polyacrylamidesolution may be up to 2% by weight, for instance, from 0.01 to 2%,suitably from 0.05 to 1.5%, often, 0.1% to 1%.

Aqueous polyacrylamide concentrates may have a concentration from 2.1 to14.9% by weight, in particular from 2.1% to 7% by wt., for example from3.1% to 6% by weight. It goes without saying, that obtaining aconcentrate of 14.9% by weight requires that the concentration of thepolyacrylamide gel used as starting material for step 5 is greater than14.9% by weight.

Step [4] Comminution of the Aqueous Polyacrylamide Gel

In course of step [4] the aqueous polyacrylamide gel is comminuted byconveying the aqueous polyacrylamide gel through at least onerelocatable comminuting unit, thereby obtaining aqueous polyacrylamidegel pieces.

The relocatable comminution unit may be a separate, relocatablecomminution unit. In another embodiment, the comminution unit may befixed to the relocatable polymerization unit, so that the relocatablepolymerization unit and the comminution unit are one relocatable unit.Such a unit is relocatable in its entirety.

The particle size of the aqueous polyacrylamide gel pieces obtained incourse of step [4] is not specifically limited. In an embodiment of theinvention, particles of aqueous polyacrylamide gel should convenientlyhave a size such that at least two dimensions are no more than 1 cm,preferably no more than 0.5 cm. Preferably three dimensions of theaqueous polyacrylamide gel pieces should be no more than 1 cm,preferably no more than 0.5 cm. There is no lower limit necessary forthe aqueous polyacrylamide gel pieces, since the smaller the pieces theeasier it will be for the polymer to dissolve. Frequently, aqueouspolyacrylamide gel pieces may have a size such that three dimensions areas low as 0.1 cm. Often the aqueous polyacrylamide gel pieces tend tohave three dimensions each of from 0.1 cm to 0.5 cm.

Basically, any kinds of comminution means maybe used for disintegratingthe aqueous polyacrylamide gel into smaller particles. Examples ofsuitable means for comminuting aqueous polyacrylamide gels includecutting devices such as knives or perforated plates, crushers, kneaders,static mixers or water-jets.

In other embodiments, the relocatable comminution unit may not bedirectly connected with the polymerization unit but distant from it andthe aqueous polyacrylamide gel is transported to the comminution unit,for example by screw conveyors or belt conveyors.

When the preferred polymerization unit P1 is used, preferably, thebottom opening (32) may be connected with the comminution unit, eitherdirectly or with a pump as outlined above in between.

FIG. 6 schematically shows such an embodiment. The aqueouspolyacrylamide gel (35) in the polymerization unit enters through thebottom opening (32) into a pump (38). The pump transports the aqueouspolyacrylamide gel into a comminution unit (34) and the comminutedpolyacrylamide gel (36) leaves the comminution unit for furtherprocessing.

Static Cutting Device

In one embodiment of the invention, the aqueous polyacrylamide gel isconveyed through a static cutting device, such as knives or metal grillsthereby obtaining smaller gel particles. A static cutting devicepreferably may belocated directly under the bottom opening (32). Inother embodiments, a pump as described above may transport thepolyacrylamide gel to a more distant static cutting device. Suitablestatic cutting devices comprise perforated plates or metal grills, suchas disclosed, for instance, in U.S. Pat. No. 4,605,689. In oneembodiment, the aqueous gel is conveyed through the static cuttingdevice or into the connection between the pump and the static cuttingdevice together with an aqueous liquid as described above, preferablywater, thereby yielding a mixture of particles of an aqueouspolyacrylamide gel in an aqueous liquid. The aqueous liquid is meteredinto the connection between the bottom opening (32) and the staticcutting device, i.e. before the gel enters into the static cuttingdevice. Preferably, not the entire amount of the aqueous liquidnecessary to dissolve the polyacrylamide gel completely and to achievethe desired concentration is added at this stage but only a portion ofit. Surprisingly, already 1% of the total amount of aqueous liquidsignificantly improves conveying the aqueous polyacrylamide gel throughthe static cutting device. It goes without saying that already someportion of the polyacrylamide gel may dissolve in the aqueous liquid,thereby obtaining a mixture of an aqueous polyacrylamide gel in adiluted polyacrylamide solution. The mixture comprising aqueouspolyacrylamide gel pieces in an aqueous liquid/a diluted acrylamidesolution is conveyed to the dissolution unit, for example through apipe.

Perforated Plate

In another embodiment of the invention, the relocatable comminution unitcomprises a perforated plate the aqueous polyacrylamide gel is conveyedthrough such perforated plate. An extruder or a screw conveyor or a pumpmay be used to generate the necessary pressure for passing theperforated plate. In course of passing through the perforated plates anumber of separate cords of aqueous acrylamide gel are formed. They maybe cut by a rotating knife or may be flushed away by means of a waterjet and conveyed to the dissolution unit.

Static Mixer

In another embodiment of the invention, the aqueous polyacrylamide gelis conveyed together with an aqueous liquid through a static mixerthereby yielding a mixture of particles of an aqueous polyacrylamide gelin an aqueous liquid. Of course also a plurality of static mixers may beused. The aqueous liquid is metered into the connection between thebottom opening (26) and the static mixer, or into the connection betweenthe pump and the static mixer, i.e. before the gel enters into thestatic mixer. In an embodiment, not the entire amount of aqueous liquidnecessary to dissolve the polyacrylamide gel completely and to achievethe desired concentration is added at this stage but only a portion ofit. It goes without saying that already some portion of thepolyacrylamide gel may dissolve in the aqueous liquid, i.e. the mixturemay be also a mixture of an aqueous polyacrylamide gel in a dilutedpolyacrylamide solution. The mixture comprising aqueous polyacrylamidegel pieces in an aqueous liquid/a diluted acrylamide solution isconveyed to the dissolution unit, for example through a pipe.

Water-Jet Cutting

In a preferred embodiment of the invention, the aqueous polyacrylamidegel is cut into pieces on aqueous polyacrylamide gel by means of awater-jet cutting unit. The water-jet cutting unit cuts the aqueouspolyacrylamide gel by means of at least one water jet at a pressure ofat least 150*10⁵ Pa thereby obtaining a mixture of particles of anaqueous polyacrylamide gel in an aqueous liquid. Of course, already someof the aqueous polyacrylamide gel may dissolve in the aqueous liquid incourse of water-jet cutting.

Preferably, the surrounding wall section of the water jet cutting unitis a tubular section, a conical section or a combination of tubular andconical sections. The aqueous polyacrylamide gel may then enter into thewater jet cutting unit from one end, pass through the cutting stage toreduce the size of the aqueous polyacrylamide gel and desirably the soformed aqueous polyacrylamide gel pieces should exit from the outlet.Aqueous liquid from the cutting stage, desirably should also exit fromthe outlet. Thus, a mixture of aqueous polyacrylamide gel pieces andwater optionally comprising dissolved polymer gel may be formed in thecutting stage.

The surrounding wall section of the water jet cutting unit may be in anysuitable orientation. Nevertheless, it is preferred that the surroundingwall section is substantially upright, with the inlet at the upper endand the outlet at the lower end. The upper end may be preferablyconnected directly with the bottom opening (3) of the polymerizationunit by suitable means.

The passage of the aqueous polyacrylamide gel may be by gravity alone ormay be fed into the water jet cutting unit under pressure, for instance,by pumping, mechanically feeding, by gas pressure or by the action of avacuum. Preferably, the aqueous polyacrylamide gel is fed into the waterjet cutting unit by means of gas or water pressure exerted on thecontents of the polymerization unit P1 forming the aqueouspolyacrylamide gel. Alternatively, or additionally, the aqueouspolyacrylamide gel is fed into the water jet cutting unit by means ofmechanical conveying devices, such as scrolls.

The at least one water-jet has a pressure of at least 150*10⁵ Pa. Thepressure may be considerably higher than this, for instance, up to10,000*10⁵ Pa. However, it is not normally necessary for the pressure tobe as high as this and lower pressures, for instance no higher than7,500*10⁵ Pa are usually adequate. In one embodiment of the invention,the pressure of the water jet in the cutting unit has a pressure of from150*10⁵ Pa to 5,000*10⁵ Pa, preferably from 200*10⁵ Pa to 2,000*10⁵ Pa,more preferably from 250*10⁵ Pa to 1000*10⁵ Pa.

Typically, the water jet would flow from a nozzle having a nozzleorifice of suitable diameter. By the term nozzle we mean a device whichis designed to control the direction or the characteristics of a fluidflow, including to increase the velocity, as it exits. In general, thenozzle orifice diameter should be from 0.1 mm to 3.00 mm, for instance,from 0.25 mm to 2.00, or from 0.25 mm to 1.00 mm, suitably from 0.30 mmto 0.90 mm, desirably from 0.40 mm 0.80 mm. It may be desirable toemploy a multiplicity of nozzles on a head in which each nozzle deliversa stream of aqueous liquid at the aforementioned pressures of at least150″10⁵ Pa. When a multiplicity of nozzles on a head is employed thenumber of nozzles may be at least 2, for instance, from 2 to 10 nozzles.The nozzles may be arranged in one plane or in different planes andangles. The nozzles may be arranged in such a way, for instance over adomed surface of the head, that the multiplicity of streams radiate outin different axises. Such a multiplicity of nozzles may be arranged suchthat the streams of aqueous liquid form an array each travelling indifferent directions.

The at least one nozzle may rotate or oscillate.

In one embodiment, the at least one nozzle oscillates. Such oscillationof the nozzle may produce a fan shaped water stream sweep pattern. Inthis embodiment of the invention, it may be of particular value toemploy a multiplicity of nozzles which can oscillate. Typically, thenumber of nozzles may be from 2 to 8, preferably from 2 to 6. It mayalso be desirable that a multiplicity of nozzles are arranged on atleast one head, each head containing from 2 to 10 nozzles. It may bedesirable for the multiplicity of heads, for instance, from 2 to 10heads, each head containing the multiplicity of nozzles, to be employed.In this case each of the heads may separately oscillate.

Such multiplicity of nozzles or multiplicity of heads each may bepositioned circumferentially with respect to the aqueous polyacrylamidegel, such that the water streams extend inwardly. The multiplicity ofnozzles and/or multiplicity of heads may be positioned evenly such thatthe distance between all adjacent nozzles is equal. Alternatively, theymay not to be evenly spaced.

Thus, when the multiplicity of nozzles or multiplicity of heads arearranged circumferentially the aqueous polyacrylamide gel would thenpass within the circumferentially positioned nozzles and be cut by themultiplicity of aqueous liquid streams. The at least one oscillatingnozzle or head may be moved by a suitable actuator mechanism.

Each oscillating nozzle may have a sweep of up to 180°. Typically, thesweep may be 30° to 180°, for instance from 35° to 75°. The exact rangeof the sweep will often depend on the exact number of nozzles employed.The oscillation frequency should for instance be up to 50 s⁻¹ (cyclesper second), typically from 0.5 s⁻¹ to 50 s⁻¹.

When the at least one nozzle, for instance, multiplicity of nozzles, orat least one head, for instance multiplicity of heads, is/are arrangedcircumferentially with respect to the aqueous polyacrylamide gel, eachof the at least one nozzles or at least one head may rotatecircumferentially about the aqueous polyacrylamide gel. When thecircumferentially arranged at least one nozzle or at least one headrotates it may be desirable that each nozzle or each head mayindependently oscillate as given above. Alternatively, it may bedesirable that when the circumferentially arranged at least one nozzleor at least one head rotates they may not oscillate. The rotation of theat least one nozzle or at least one head may be achieved by a suitabledrive mechanism.

In another preferred embodiment of the invention, the at least onenozzle rotates and the stream of aqueous liquid generated forms acircular sweep pattern. The at least one nozzle may be a multiplicity ofnozzles housed on at least one head. Such at least one rotating nozzlemay be rotated by the action of a suitable motorized drive mechanism.

It may be desirable to employ more than one rotating nozzle, forinstance, a multiplicity of nozzles housed on at least one head.However, it is usually only necessary to employ one rotating nozzle orwhere more than one nozzle is employed the multiplicity of nozzles arearranged on one head.

In one embodiment of the invention, the at least one rotating nozzle, orat least one head is mounted centrally and the aqueous liquid streamextends substantially perpendicular to the axis of the direction of theincoming aqueous polyacrylamide gel. In this form the aqueous liquidstream sweep pattern is disc shaped. In an adaptation of this preferredaspect the rotating nozzle or head, which is/are mounted centrally, maygenerate at least one stream of liquid which is not perpendicular to thedirection of the incoming aqueous polyacrylamide gel, but instead isangled such that the at least one aqueous liquid stream sweep pattern isa cone shaped, for instance, an upright cone where the at least oneaqueous liquid stream is angled downwards, or an inverted cone where theat least one aqueous liquid stream is angled upwards. Where the at leastone aqueous liquid stream is angled either upwards or downwards it ispreferred that the angle is no more than 50° up or down from theposition which is perpendicular to the direction of the incoming aqueouspolyacrylamide gel. Preferably this angle should be from 5° to 45°, morepreferably from 10° to 35°, particularly from 15° to 25°.

In a further embodiment of the invention, the at least one rotatingnozzle or rotating head is not mounted centrally but off center. Forinstance, where the cutting stage is contained in a surrounding wallsection the rotating nozzle may be located at or close to the wall ofthe surrounding wall section. Typically, the nozzle or head would beorientated such that it generates at least one eccentric aqueous streamsweep pattern.

The rotating nozzle or rotating head may rotate at a frequency of up to3000 rpm (revolutions per minute (i.e. 50 s⁻¹ cycles per second)). Therotational frequency may be selected by the skilled artisan. A higherrotational frequency, for example a rotational frequency from 500 rpm to3000 rpm) may by trend tear the aqueous polyacrylamide gel into smallerparts while a smaller rotational frequency, for example from 10 rpm toless than 500 ppm, preferably 20 rpm to 200 rpm more properly cuts theaqueous polyacrylamide gel.

Desirably, the water-jet cutting unit will divide the aqueouspolyacrylamide gel into numerous smaller sized pieces. The aqueouspolyacrylamide gel pieces should conveniently have a size such that atleast two dimensions are no more than 2 cm, preferably no more than 1cm, more preferably no more than 0.5 cm. Preferably three dimensions ofthe aqueous polyacrylamide gel pieces should be no more than 2 cm,preferably no more than 1 cm, preferably no more than 0.5 cm. There isno lower limit necessary for the aqueous polyacrylamide gel pieces,since the smaller the pieces the easier it will be for the polymer todissolve. In one embodiment, the aqueous polyacrylamide gel pieces havethree dimensions each of from 0.1 to 1.5 cm.

The water-jet cutting unit may also comprise a sieve tray beneath the atleast one stream of aqueous liquid. This is intended to preventoversized aqueous polyacrylamide gel lumps from passing into the nextstage. The sieve tray should have openings of a size corresponding tothe maximum size of aqueous polyacrylamide gel pieces which should beallowed to pass to the next stage. Suitably the sieve tray may be a meshformed by a plurality of inter-meshing wires or bars. Alternatively, thesieve tray may be formed as a surface with a plurality of holes cuttherein, for instance, analogous to a colander. Typically, the sievetray should be a static device. It should extend to cover the whole areabelow where the aqueous polyacrylamide gel cutting is taking place.Preferably, the sieve tray may be affixed to the surrounding wallsection. In embodiments of the present invention additional streams ofaqueous liquid are directed at the surface of the sieve tray in order tofacilitate the size reduction of the oversized aqueous polyacrylamidegel lumps captured by the tray. It may be desirable to employ one ormore aqueous liquid streams of high-pressure, for instance, of at least150′10⁵ Pa in order to facilitate the cutting of the oversized aqueouspolyacrylamide gel lumps such that the aqueous polyacrylamide gel is cutinto small enough pieces to pass through.

Desirably, a curtain of aqueous liquid is provided on the inside of thesurrounding wall section. This curtain of aqueous liquid may helpprevent aqueous polyacrylamide gel from sticking to the wall of thesurrounding wall section and reduce friction of the moving polymerthereby reducing necessary static pressure or avoiding additionalmechanical means to move the polymer towards the cutting area. Suchcurtain of aqueous liquid may be produced by providing a secondaryaqueous liquid supply. Typically, the pressure of the aqueous liquidshould be below 30 bar, for instance, from 3 bar to 20 bar, desirablyfrom 5 bar to 10 bar. The water may be fed to a ring main, in the formof an annulus, and mounted on the inside of the surrounding wallsection. In order to be most effective, the ring main or annulus shouldbe mounted at or close to the top of the surrounding wall section toprovide the maximum protection by the curtain of water. Desirably theaqueous liquid flows from the ring main or annulus down the innersurface of the wall of the surrounding wall section as a curtain.

FIGS. 7 to 10 represent schematically several embodiments of a water-jetcutting unit for use in the present invention.

FIG. 7 illustrates schematically a water-jet cutting unit for cuttingthe aqueous polyacrylamide gel. The device comprises a surrounding wallsection (101), in this case a tubular wall, surrounding a centrallymounted nozzle (102) which rotates and is driven by a motor (103) orpropelled by the flowing aqueous liquid, which forms the stream. Thenozzle is supported on a fixed mounting (104). A high-pressure stream ofaqueous liquid (105) is ejected perpendicular to the axis of the deviceand rotates as the nozzle rotates. The stream of aqueous liquid forms acircular disc pattern as the nozzle rotates. The nozzle is fed from aaqueous liquid feed line (106) supplied by a high pressure aqueousliquid source (107). A sieve tray (108) is located beneath the stream ofwater and prevents oversized polymer lumps from passing. A secondaryaqueous liquid supply (109) of low pressure is fed into a ring main(110), in the form of an annulus, located at the upper end of thetubular wall. Aqueous liquid flows out of the annulus to form a watercurtain (111), which prevents aqueous polyacrylamide gel from stickingto the tubular wall. Aqueous polyacrylamide gel (113) enters the tubularwall from above and passes down the device where it is cut by thehigh-pressure water stream to form cut hydrated polymer pieces which aresmall enough to pass through the sieve tray and then the cut aqueouspolyacrylamide gel pieces (114) exit from the bottom of the device.

FIG. 8 illustrates a device analogous to the device of FIG. 7 except thenozzle (102) provides a high-pressure stream of water which is angleddownwards (105A) to form a conical pattern as the nozzle rotates. Thesieve tray is in the shape of an upright cone (108A). All other featuresare as in the case of FIG. 7.

FIG. 9 illustrates a device analogous to the device of FIG. 7 except thenozzle (102) provides a high-pressure stream of water which is angledupwards (105B) to form a conical pattern as the nozzle rotates. Thesieve tray is in the shape of an inverted cone (108B). All otherfeatures are as in the case of FIG. 7.

FIG. 10 illustrates a device analogous to the device of FIG. 7 exceptthe nozzle (102) is positioned off center to provide an eccentrichigh-pressure water stream (105) sweep pattern. All other features areas in the case of FIG. 7.

Combinations

The described methods of comminuting the aqueous polyacrylamide gel mayalso combined with each other.

In one embodiment of the invention, the relocatable comminution unitcomprises at least a water-jet cutting device and a static cuttingmember. The at least one static cutting member may for instance be oneor more knives, blades, cutting wires or any combination thereof. In oneform the at least one cutting member may consist of a multiplicity ofknives or blades mounted on the wall of the tubular sectioncircumferentially with the knives or blades extending inwardly. Inanother form the at least one cutting member may be knives or bladesmounted from a central position with the knives or blades extending outradially. In a further form the at least one cutting member may be amesh of knives, blades or cutting wires. Typically, the static cuttingmember, where employed, should extend over the whole cross-section ofthe surrounding wall section. Suitably, the aqueous polyacrylamide gelmay be cut by contacting the at least one static cutting member beforecontacting the at least one stream of aqueous liquid.

FIG. 11 illustrates schematically a water-jet cutting unit combined withstatic cutting means. The device comprises a surrounding wall section(101), in this case a tubular wall, into which the aqueouspolyacrylamide gel (113) enters from the top. A mesh of cutting blades(112) initially cuts the hydrated polymer into strands as it descends.High-pressure water streams (105) are ejected from nozzles (102) thatare positioned circumferentially. The nozzles each oscillate laterallyto each generate a fan shaped water stream sweep pattern (115) which cutthe polymer strands as they descend. The oscillation of the nozzles isdriven by an actuator (not shown) in each case. The aqueouspolyacrylamide pieces (114) exit through the bottom of the device.

In another embodiment, water-jet cutting may be combined with staticmixing. For that purpose, the aqueous mixture comprising pieces ofpolyacrylamide gel leaving the water-jet cutting unit is conveyedthrough at least one static mixer. Additional aqueous liquid may beadded to the mixture, before it enters into the at least one staticmixer.

In another embodiment, water-jet cutting is combined with both, staticcutting means and a static mixer. The combination with static cuttingmeans has already been described above. Thereafter, the aqueous mixturecomprising pieces of polyacrylamide gel leaving the comminution unitcomprising a water-jet cutting step and a static cutting step isconveyed through at least one static mixer. Additional aqueous liquidmay be added to the mixture, before it enters into the at least onestatic mixer.

In one embodiment, comminuting the aqueous polyacrylamide gel is carriedout by at least one means selected from rotating water-jets, rotatingknives or and a hole perforation plate. Preferably, a combination of atleast one hole perforation plate and rotating water-jets or at least onehole perforation plate and rotating knives may be used.

In other embodiments, the comminution unit comprises a combination ofwater-jet cutting and a hole perforation plate. The hole perforationplate comprises holes. The shape of the holes is not specificallylimited. Examples comprise circular holes, ellipsoidal holes, triangularholes, quadrangular holes such as quadratic, rectangular, or rhombicholes, pentagonal holes, hexagonal holes or star-like holes but alsolongitudinal holes such as slots. The holes may be cylindrical holes butthey may also be conical.

The dimensions of the holes are not specifically limited. However,preferably at least one dimension of the holes should be from 0.5 to 5mm. In one embodiment of the invention, the hole perforation platecomprises circular holes having a diameter from 0.5 to 5 mm, for examplefrom 1 mm to 3 mm.

The aqueous polyacrylamide is conveyed from the polymerization unitthrough the hole perforation plate. One or more rotating nozzles forwater-jets are mounted above or below the hole perforation plate.

One embodiment of such a combination is schematically shown in FIG. 12.FIG. 12 schematically shows a polymerization unit having an uppercylindrical part (120), a lower conical part (121) and a bottom opening(125) which may be opened and closed. In the embodiment shown, thepolymerization unit is connected directly with a comminution unitcomprising a hole perforation plate. In other embodiments, one pump asdescribed above may be used to transport the aqueous polyacrylamide gelfrom the bottom opening (121) to the comminution unit. One rotatingnozzle for water-jets is mounted below the hole perforation plate. Theaqueous polyacrylamide gel is removed from the polymerization unit byopening the bottom opening (125) and applying pressure onto the uppersurface of the aqueous polyacrylamide gel. The polyacrylamide gel isconveyed through the opened bottom opening and the hole perforationplate. In other embodiments, it is conveyed, polyacrylamide gel isconveyed through the opened bottom opening to a pump as described aboveand from the pump it is conveyed through the hole perforation plate. Thehole perforation plate generates strings of aqueous polyacrylamide gel(“spaghetti”) which are cut into small pieces by the water-jets.

FIG. 13 shows a similar embodiment except that not one two nozzles aremounted below the hole perforation plate. Of course, also more than twonozzles may be used, for example 4 nozzles.

FIGS. 14 and 15 show similar embodiments in which the nozzle(s) forwater-jets are mounted above and not below the hole perforation plate.

FIG. 16 shows an alternative embodiment comprising a rotating knifemounted below the hole perforation plate for cutting. Its function isthe same a detailed above (FIGS. 12 and 13), except that a mechanicalknife and not water-jets are used for cutting the strings ofpolyacrylamide gel. In this embodiment, water (127) is added into thecutting space below the hole perforation plate. The water may be addedthrough one or more than one water inlets. The amount of water into thecutting space may already up to 50% by weight of the entire amount ofwater needed for dissolving the aqueous polyacrylamide gel, for examplefrom 5% to 25% by weight.

Step [5] Dissolution

The dissolution of the aqueous polyacrylamide gel pieces generated incourse of step [4] in an aqueous liquid is conducted in a relocatabledissolution unit. Basically, any kind of relocatable dissolution unitmay be used.

Examples of suitable relocatable dissolution units comprise stirredvessels. A dissolution unit may only comprise one vessels or it maycomprise more than one vessel which may be operated in series or inparallel. Mixing may also be achieved by flowing the contents of thedissolution vessel out through a conduit and then recirculating backinto the mixing vessel. Other examples comprise relocatable dissolutionunits comprising a combination of static mixers with unstirred vesselsor in-line dispersing such as rotor-stator units.

Unstirred vessels or unstirred vessels in combination with otherequipment such as static mixers are in particular useful, when thedesired concentration of the polyacrylamide solution is higher, forexample when the aqueous polyacrylamide solution is a concentrate asindicated above, for example a concentrate having a concentration of3.1% to 6% by weight. Dissolution may be performed by conveying thecomminuted aqueous polyacrylamide gel through a static mixer or aplurality of static mixers together with sufficient aqueous liquid andthereafter the mixture is filled into an unstirred vessel and allowed tostand in order to finalize dissolution.

In one embodiment of the invention, the aqueous polyacrylamide gelpieces are dissolved in the aqueous liquid by passing the aqueouspolyacrylamide gel pieces of step [4], preferably a mixture of aqueouspolyacrylamide gel pieces in an aqueous liquid into a relocatabledissolution comprising at least a dissolution vessel and means formixing the polyacrylamide gel with the aqueous liquid. Aqueous liquid isadded to the dissolution vessel. The amount depends on the amount ofaqueous liquid already added to the aqueous polyacrylamide gel in thepreceding comminution step and the desired concentration of the finalpolyacrylamide solution.

Examples of means for mixing comprise one or more impellers or stirrerswhich optionally may be combined with static mixing devices. Mixing mayalso be achieved by flowing the contents of the dissolution vessel outthrough a conduit and then recirculating back into the mixing tank. Thedissolution unit may also comprise two or more than two dissolutionvessels connected in series. The volume of the dissolution vessel is notspecifically limited and may range from 10 m³ to 150 m³, for examplefrom 20 m³ to 50 m³ per vessel.

FIG. 17 schematically represents one embodiment of a relocatabledissolution unit. The unit comprises a frame (40) and a dissolutionvessel (41) filled with aqueous liquid and aqueous polyacrylamide gelpieces. For mixing the contents of the dissolution vessel (51), thedissolution unit comprises two stirrers (42) and (43). It goes withoutsaying that also other numbers of stirrers and other constructions ofstirrers than those depicted in FIG. 14 may be used. By the way ofexamples one agitator shaft may be equipped with two stirrers indifferent positions.

The aqueous polyacrylamide gel pieces, preferably a mixture of aqueouspolyacrylamide gel pieces and aqueous liquid/aqueous polyacrylamidesolution is filled into the dissolution vessel through an opening (44)and the polyacrylamide solution may be removed through the line (45).

In another embodiment, two or more dissolution units may be connected inseries. In embodiments of the invention 2 to 15, for example 5 to 12dissolution units may be connected in series. The aqueous polyacrylamidegel pieces, preferably the mixture of aqueous polyacrylamide pieces arefilled in the first dissolution vessel and mixed with aqueous liquid.The mixture is continuously transported into at least a seconddissolution unit for further dissolution. It may be transferred fromthere into a third dissolution unit. From the last dissolution unitaqueous polyacrylamide solution may be removed.

It is also possible, that not separate relocatable dissolution units areused but that two or more dissolution vessels may be connected in seriesin just one frame.

In another embodiment, at least two the relocatable dissolution units,preferably at least three relocatable dissolution may be connected in acyclical manner, i.e. they are connected in series and the last one isconnected again with the first one.

FIG. 18 schematically represents an embodiment in which two relocatabledissolution units are connected in series. The contents of the firstdissolution unit (45) is added to the next dissolution unit thepolyacrylamide solution may be removed through the line (46). Additionalaqueous liquid may also be added to the second dissolution unit.

In another embodiment, a relocatable dissolution unit is a dissolutionunit fixed on a truck.

In another embodiment, the aqueous polyacrylamide solution may befurther diluted for application after carrying out step [5] in a seconddilution step.

After carrying out step [5], the aqueous polyacrylamide solution may bedirectly transferred to the site where it is used, i.e. to an oil wellfor injection. In other embodiments the aqueous may be storedtemporarily at location B before using it.

For such temporary storage, a storage vessel or a series of storagevessels may be used. Storing the solution in particular is advantageousto make the necessary analytics and the quality control.

For transporting the aqueous polyacrylamide solution obtained in courseof step [5]-either directly from the dissolution unit or temporarystorage vessels to the site-of-use several options exist depending onthe location of the site-of-use.

In one embodiment, the transfer may simply be carried out by means ofpiping or any other suitable conduit.

For transporting the aqueous polyacrylamide solution to more distantsites-of-use, also pipelines may be used. In another embodiment, theaqueous solution is transported from the modular plant to thesite-of-use using a suitable transport unit. Examples of suitabletransport units comprise for instance road tankers or tank containers.

In one embodiment of the invention, step [5] is carried out in such amanner that a concentrate as defined above is obtained, i.e. an aqueouspolyacrylamide solution having a concentration from 2.1 to 14.9% byweight, in particular from 2.1% to 7% by wt., for example from 3.1% to6% by weight. Thereafter, such concentrate is transported to thesite-of-use using a suitable transport unit, for instance a transportunit as described above. At the site-of-use, the concentrate is removedfrom the transport unit, for instance by pumping and either useddirectly or alternatively diluted with additional aqueous liquid therebyobtaining an aqueous polyacrylamide solution having a lowerconcentration, for example a concentration from 0.01% by weight to 2% byweight. Transporting a concentrate has the advantage of transportingless water compared to transporting a dilute solution which reducestransport cost. The concentrates as described above may still be viscosfluids or even solid but usually they are still pumpable, so that theycan be easily removed from the transport units.

By the way of example, in such an embodiment, the modular plant may belocated at a more central point of an oil field and serves a number ofdifferent oil wells with polyacrylamide concentrate. The distancebetween the modular plant and the sites-of-use may for example be from 1to 500 km or from 10 km to 300 km.

Modification of the Polyacrylamides

In one embodiment of the invention, the polyacrylamides maysimultaneously by modified in course of steps [4] and [5].

For that purpose, suitable agents for modifying the polymers may beadded to the aqueous liquid used for dissolving the aqueouspolyacrylamide gel. In other embodiments, such agents may be addedseparately, preferably as aqueous solution.

In one embodiment of the invention, the polyacrylamides may be partiallyhydrolyzed thereby obtaining polyacrylamides comprising also —COOHgroups or salts thereof. In certain embodiments, about 30 mol % of theamide groups may be hydrolyzed to carboxylic groups. Partiallyhydrolyzed polyacrylamides are known in the art. For that purpose, basessuch as NaOH are added to the aqueous liquid.

In another embodiment, hydroxylamine and a base may be added to theaqueous liquid thereby obtaining polyacrylamides in which a part of theamide groups are converted to hydroxamic acid groups.

Measurement and Control

In one embodiment, the modular, relocatable plant comprises a centralprocess measuring and control technology unit. Preferably, the processmeasuring and control technology unit is connected with all units of themodular, relocatable plant, thereby enabling a central process controlsimilar to fixed plants. In one embodiment, all connections withmeasuring and control instruments of a certain unit, e.g. thedissolution unit, the monomer storage units or the polymerization unitsare bundled in one cable, for example BUS technology, so that they maybe easily plugged together. Of course, also other connectingtechnologies are possible, for example radio links.

Modular, Relocatable Plant

In a further embodiment, the present invention relates to a modular,relocatable plant for manufacturing aqueous polyacrylamide solutions bypolymerizing an aqueous solution comprising at least acrylamide therebyobtaining an aqueous polyacrylamide gel and dissolving said aqueouspolyacrylamide gel in an aqueous liquid, comprising at least

-   -   a relocatable storage unit for an aqueous acrylamide solution,    -   optionally relocatable storage units for water-soluble,        monoethylenically unsaturated monomers different from        acrylamide,    -   a relocatable storage unit for polymerization initiators,    -   a relocatable monomer make-up unit for preparing an aqueous        monomer solution comprising at least water and acrylamide,    -   a relocatable polymerization unit for polymerizing the aqueous        monomer solution in the presence of polymerization initiators,    -   a relocatable comminution unit for comminuting aqueous        polyacrylamide gel to pieces of aqueous polyacrylamide gel,    -   a relocatable dissolution unit for the dissolution of pieces of        aqueous polyacrylamide gel in aqueous fluids,

Details of the individual units of the plant, including preferredembodiments, have already been described above and we refer to therespective passages.

In one preferred embodiment, the relocatable comminution unit comprisesat least means selected from rotating water-jets, rotation knives andhole perforation plates.

In another preferred embodiment, the modular, relocatable plantcomprises relocatable storage units for water-soluble, monoethylenicallyunsaturated monomers different from acrylamide.

In a preferred embodiment, acrylamide is also manufactured in themodular, relocatable plant by hydrolyzing acrylonitrile in water in thepresence of a biocatalyst capable of converting acrylonitrile toacrylamide.

The present invention therefore furthermore relates to a modular,relocatable plant for manufacturing aqueous polyacrylamide solutions bypolymerizing an aqueous solution comprising at least acrylamide therebyobtaining an aqueous polyacrylamide gel and dissolving said aqueouspolyacrylamide gel in water, comprising at least

-   -   a relocatable storage unit for acrylonitrile,    -   a relocatable bioconversion unit for hydrolyzing acrylonitrile        in water in the presence of a biocatalyst capable of converting        acrylonitrile to acrylamide,    -   a relocatable unit for removing the biocatalyst from an aqueous        acrylamide solution,    -   a relocatable storage unit for an aqueous acrylamide solution,    -   optionally relocatable storage units for water-soluble,        monoethylenically unsaturated monomers different from        acrylamide,    -   a relocatable storage unit for polymerization initiators,    -   a relocatable monomer make-up unit for preparing an aqueous        monomer solution comprising at least water and acrylamide,    -   a relocatable polymerization unit for polymerizing the aqueous        monomer solution in the presence of polymerization initiators.    -   a relocatable comminution unit for comminuting aqueous        polyacrylamide gel to pieces of aqueous polyacrylamide gel,    -   a relocatable dissolution unit for the dissolution of pieces of        aqueous polyacrylamide gel in aqueous fluids.

Details of the individual units of the plant have already been describedabove and we refer to the respective passages. As outlined above, thecomminution unit may be a separate, relocatable comminution unit or itmay be fixed to the polymerization unit.

Use of the Aqueous Polyacrylamide Solutions

The aqueous polyacrylamide solutions manufactured according to thepresent invention may be used for various purposes, for example formining applications, oilfield applications, water treatment, waste watercleanup, paper making or agricultural applications.

For the application, the aqueous polyacrylamide solutions may be used assuch or they may be formulated with further components. The specificcomposition of aqueous polyacrylamide solutions is selected by theskilled artisan according to the intended use of the polyacrylamidesolution.

Oilfield Applications

Examples of oilfield applications in which the aqueous polyacrylamidesolutions manufactured according to the present invention may be usedinclude enhanced oil recovery, oil well drilling or the use as frictionreducers, for example friction reducers for fracturing fluids.

Enhanced Oil Recovery

In one embodiment of the invention, the aqueous polyacrylamide solutionsmanufactured according to the present invention are used for enhancedoil recovery.

Accordingly, the present invention also relates a method for producingmineral oil from underground mineral oil deposits by injecting anaqueous fluid comprising at least an aqueous polyacrylamide solutioninto a mineral oil deposit through at least one injection well andwithdrawing crude oil from the deposit through at least one productionwell, wherein the aqueous polyacrylamide solution is prepared by theprocess for producing an aqueous polyacrylamide solution as describedabove. Details of the process have already been disclosed above.

For the method of enhanced oil recovery, at least one production welland at least one injection well are sunk into the mineral oil deposit.In general, a deposit will be provided with a plurality of injectionwells and with a plurality of production wells. An aqueous fluid isinjected into the mineral oil deposit through the at least one injectionwell, and mineral oil is withdrawn from the deposit through at least oneproduction well. By virtue of the pressure generated by the aqueousfluid injected, called the “polymer flood”, the mineral oil flows in thedirection of the production well and is produced through the productionwell. In this context, the term “mineral oil” does not of course justmean a single-phase oil; instead, the term also encompasses thecustomary crude oil-water emulsions.

The aqueous fluid for injection comprises the aqueous poly acrylamidesolution prepared by process according to the present invention. Detailsof the process have been disclosed above.

In one embodiment, the modular plant according to the present inventionmay be at an injection well to be treated with aqueous polyacrylamidesolutions or close to such an injection well. In another embodiment, themodular plant may be in between a plurality of such injection wells orat one of them and the aqueous polyacrylamide solution is distributedfrom there to all injection wells, for example by means of pipelines.

The aqueous acrylamide solution obtained may be used as such or it maybe mixed with further components. Further components for enhanced oilrecovery fluids may be selected by the skilled artisan according tohis/her needs.

For enhanced oil recovery, a homopolymer of acrylamide may be used,however preferably water-soluble copolymers comprising at least 10%,preferably at least 20%, and more preferably at least 30% by weight ofacrylamide and at least one additional water-soluble, monoethylenicallyunsaturated monomer different from acrylamide are used. Suitablewater-soluble comonomers have already been mentioned above and we referto the disclosure above.

In one embodiment, water-soluble comonomers may be selected fromwater-soluble, monoethylenically unsaturated monomers comprising atleast one acid group, or salts thereof. The acidic groups are preferablyselected from the group of —COOH, —SO₃H and —PO₃H₂ or salts thereof.Preference is given to monomers comprising COOH groups and/or —SO₃Hgroups or salts thereof. Suitable counterions have already beenmentioned above. Examples of such comonomers comprise acrylic acid,methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaricacid, vinylsulfonic acid, allylsulfonic acid,2-acrylamido-2-methylpropanesulfonic acid (ATBS),2-methacrylamido-2-methylpropane-sulfonic acid,2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutane-sulfonicacid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonicacid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic acids and(meth)acryloyloxyalkyl-phosphonic acids.

In a preferred embodiment, acrylic acid and/or ATBS or salts thereof maybe used as comonomers.

In such copolymers, the amount of acrylamide usually is from 20% by wt.to 90% by wt. and the amount of acrylic acid and/or ATBS or saltsthereof is from 10% by wt. to 80% by wt., relating to the amount of allmonomers in the copolymer. Preferably, the amount of acrylamide is from60% by wt. to 80% by wt. and the amount acrylic acid and/or ATBS orsalts thereof is from 20% by wt. to 40% by wt.

In another embodiment, the copolymers to be used for enhanced oilrecovery comprise at least one water-soluble, monoethylenicallyunsaturated monomer comprising at least one acid group, or saltsthereof, preferably acrylic acid and/or ATBS or salts thereof, and atleast one associative monomer. Examples of associative monomers havealready been disclosed above. In one embodiment, at least oneassociative monomer of the general formula (III), (IV), or (V) is used,preferably at least one associative monomer of the general formula (V).Preferred embodiments of the associative monomers (III), (IV), and (V)have already been disclosed above and it is explicitly referred to thatdescription.

In such polyacrylamides, the amount of acrylamide usually is from 40% bywt. to 89.9% by wt., the amount of acrylic acid and/or ATBS or saltsthereof is from 10% by wt. to 59.9%, and the amount of associativemonomers is from 0.1 to 5% by wt., relating to the amount of allmonomers in the copolymer.

In one embodiment, the polyacrylamides for EOR comprise 45% to 55% byweight of acrylamide, 0.1 to 5%, preferably 0.1 to 2% by weight of atleast one associative monomer of the general formula (V) mentionedabove, including the preferred embodiments, and 40 to 54.9% by weight ofacrylic acid or salts thereof.

The aqueous fluid for injection can be made up in freshwater or else inwater comprising salts, such as seawater or formation water. As alreadyoutlined above, water comprising salts may already be used fordissolving the aqueous polyacrylamide gel. Alternatively, thepolyacrylamide gel may be dissolved in fresh water, and the solutionobtained can be diluted to the desired use concentration with watercomprising salts.

The aqueous injection fluid may of course optionally comprise furthercomponents. Examples of further components include biocides,stabilizers, free-radical scavengers, initiators, surfactants,cosolvents, bases and complexing agents.

The concentration of the copolymer in the injection fluid is fixed suchthat the aqueous formulation has the desired viscosity for the end use.The viscosity of the formulation should generally be at least 5 mPas(measured at 25° C. and a shear rate of 7 s⁻¹), preferably at least 10mPas.

In general, the concentration of the polyacrylamide in the injectionfluid is 0.02 to 2% by weight based on the sum total of all thecomponents in the aqueous formulation. The amount is preferably 0.05 to0.5% by weight, more preferably 0.1 to 0.3% by weight and, for example,0.1 to 0.2% by weight.

Friction Reducers for Hydraulic Fracturing

In another embodiment of the invention, the aqueous polyacrylamidesolutions manufactured according to the present invention are used asfriction reducers in hydraulic fracturing applications.

Hydraulic fracturing involves injecting fracturing fluid through awellbore and into a formation under sufficiently high pressure to createfractures, thereby providing channels through which formation fluidssuch as oil, gas or water, can flow into the wellbore and thereafter bewithdrawn. Fracturing fluids are designed to enable the initiation orextension of fractures and the simultaneous transport of suspendedproppant (for example, naturally-occurring sand grains, resin-coatedsand, sintered bauxite, glass beads, ultra-lightweight polymer beads andthe like) into the fracture to keep the fracture open when the pressureis released.

In one embodiment of hydraulic fracturing, fracturing fluids having ahigh viscosity are used. Such a high viscosity may be achieved bycrosslinked polymers, such as crosslinked guar. Such a high viscosity isnecessary to ensure that the proppants remain distributed in thefracking fluid and don't sediment, for example already in the wellbore.

In another embodiment of hydraulic fracturing, also known as “slickwaterfracturing”, fluids having only a low viscosity are used. Such fluidsmainly comprise water. In order to achieve proppant transport into theformation, the pumping rates and the pressures used are significantlyhigher than for high-viscosity fluids, thereby causing turbulent flow.The turbulent flow of the fracking fluid causes significant energy lossdue to friction. In order to avoid or at least minimize such frictionlosses, high molecular weight polyacrylamides may be used which changeturbulent flow to laminar flow.

Accordingly, in another embodiment the present invention relates to amethod of fracturing subterranean formations by injecting an aqueousfracturing fluid comprising at least an aqueous base fluid, preferablywater, proppants and a friction reducer through a wellbore into asubterranean formation at a pressure sufficient to flow into theformation and to initiate or extend fractures in the formation, whereinthe friction reducer comprises an aqueous polyacrylamide solutionprepared by the process for producing an aqueous polyacrylamide solutionin a modular plant as described above. Details of the manufacturingprocess have already been disclosed above. Examples of aqueous basefluids comprise fresh water, brines, sea water, formation water treatedwater or mixtures thereof.

In a preferred embodiment of the present invention, the aqueouspolyacrylamide solution has a concentration from 2.1 to 14.9% by weight,preferably from 2.1 to 10% by weight, in particular from 2.1% to 7% bywt., and for example from 3.1% to 6% by weight. The concentrate may bepreferably used as such, i.e. without further dilution on-site. Forexample, it may be feeded into the blenders which are typically used formixing fracturing fluids. The transport of the concentrate maypreferably be carried out by filling the concentrate into a suitabletransport unit, transporting the transport unit to the site-of-use andremoving the concentrate form the transport unit, for example bypumping. The transport unit may have a volume from 1 m³ to 40 m³, inparticular 5 m³ to 40 m³, for example 20 m³ to 30 m³. Examples ofsuitable transport units comprise vessels comprising at least oneopening or tank containers.

Mining Applications

In one embodiment, the method for preparing an aqueous polyacrylamidesolution according to the present invention is carried out in areaswhere mining, mineral processing and/or metallurgy activities takesplace. Consequently, the aqueous polyacrylamide solution as productobtained by the method of the present invention is preferably used forapplications in the field of mining, mineral processing and/ormetallurgy and the method for preparing the aqueous polyacrylamidesolution is preferably used at the plant of the respective industry.

Preferably, mining activities comprises extraction of valuable mineralsor other geological materials from certain deposits. Such deposits cancontain ores, for example metal containing ores, sulfidic ores and/ornon-sulfidic ores. The ores may comprise metals, coal, gemstones,limestone or other mineral material. Mining is generally required toobtain any material in particular mineral material that cannot be grownthrough agricultural processes, or created artificially in a laboratoryor factory. The aqueous polyacrylamide solution according to the presentinvention is preferably used to facilitate the recovery of mineralmaterial, for beneficiation of ores and for further processing of oresto obtain the desired minerals or metals.

Typically, mining industries, mineral processing industries and/ormetallurgy industries are active in the processing of ores and in theproduction of for example alumina, coal, iron, steel, base metals,precious metals, diamonds, non-metallic minerals and/or areas whereaggregates play an important role. In such industries, the method of thepresent invention and the obtained homo- or copolymer of acrylamide canbe used for example

-   -   at plants for alumina production, where alumina is extracted        from the mineral bauxite using the Bayer caustic leach process,    -   at plants where the coal washing process demands a closed water        circuit and efficient tailings disposal to satisfy both economic        and environmental demands,    -   at plants for iron and steel production, where the agglomeration        of fine iron concentrates to produce pellets of high quality is        a major challenge for the iron ore industry,    -   at plants for base metal production, where flocculants find        several uses in base metal production,    -   at plants for precious metals production, where reagents are        used to enhance the tailings clarification process allowing the        reuse of clean water,    -   at diamond plants, where efficient water recovery is paramount        in the arid areas where diamonds are often found,    -   at plants for non-metallic mineral production where reagents        enhance water recovery or aid the filtration processes to        maximize process efficiency,    -   at plants where aggregates have to be produced and flocculants        and filter aids are needed to enhance solid/liquid separation.

Accordingly, the present invention relates to the use of an aqueouspolyacrylamide solution for mining, mineral processing and/or metallurgyactivities comprising the use for solid liquid separation, for tailingsdisposal, for polymer modified tailings deposition, for tailingsmanagement, as density and/or rheology modifier, as agglomeration aid,as binder and/or for material handling, wherein the aqueouspolyacrylamide solution is prepared at the plant of the respectiveindustry, comprising for example the following steps:

hydrolyzing acrylonitrile in water in presence of a biocatalyst capableof converting acrylonitrile to acrylamide so as to obtain an acrylamidesolution,

-   -   polymerizing the acrylamide solution so as to obtain a        polyacrylamide gel, and    -   dissolving the polyacrylamide gel by addition of water so as to        obtain an aqueous polyacrylamide solution.

For the mining, mineral processing and/or metallurgy activities ahomopolymer of acrylamide for example can be used. Further preferred arealso copolymers of acrylamide. Such copolymers of acrylamide can beanionic, cationic or non-ionic. Anionic copolymers are for exampleco-polymers of acrylamide with increasing proportions of acrylategroups, which give the polymers negative charges, and thus anionicactive character, in aqueous solution. Anionic copolymers of acrylamidecan in particular be used for waste water treatment in metallurgy likeiron ore plants, steel plants, plants for electroplating, for coalwashing or as flocculants. Non-ionic polymers and/or copolymers ofacrylamide can be used for example as nonionic flocculants suitable assettlement aids in many different mineral processing applications andare particularly effective under very low pH conditions, as encounteredfor example in acidic leach operations. Cationic copolymers ofacrylamide have in particular an increasing proportion of cationicmonomers. The cationic groups, which are thus introduced into thepolymer, have positive charges in aqueous solution.

It is preferred, that the polymer obtained from the method of thepresent invention is used as flocculant in a process in which individualparticles of a suspension form aggregates. The polymeric materials ofthe present invention forms for example bridges between individualparticles in the way that segments of the polymer chain adsorb ondifferent particles and help particles to aggregate. Consequently, thepolymers of the present invention act as agglomeration aid, which may bea flocculant that carries active groups with a charge and which maycounterbalance the charge of the individual particles of a suspension.The polymeric flocculant may also adsorb on particles and may causedestabilization either by bridging or by charge neutralization. In casethe polymer is an anionic flocculant, it may react against a positivelycharged suspension (positive zeta potential) in presence of salts andmetallic hydroxides as suspension particles, for example. In case thepolymer of the present invention is for example a cationic flocculant,it may react against a negatively charged suspension (negative zetapotential) like in presence of for example silica or organic substancesas suspension particles. For example, the polymer obtained from themethod of the present invention may be an anionic flocculant thatagglomerates clays which are electronegative.

Preferably, the method of the present invention and the obtained polymerand/or copolymer of acrylamide (polyacrylamide) is used for example inthe Bayer process for alumina production. In particular, thepolyacrylamide can be used as flocculant in the first step of theBayer-Process, where the aluminum ore (bauxite) is washed with NaOH andsoluble sodium aluminate as well as red mud is obtained. Advantageously,the flocculation of red mud is enhanced and a faster settling rate isachieved when acrylamide polymers and/or co-polymers are added. As redmud setting flocculants, polyacrylamide may be used for settlingaluminum red mud slurries in alumina plants, provides high settlingrates, offers better separation performance and reduces suspended solidssignificantly. Also the liquor filtration operations are improved andwith that the processing is made economically more efficient. It isfurther preferred that the polyacrylamides are used in decanters, inwashers, for hydrate thickening, for green liquor filtration, as crystalgrowth modifiers, as thickener and/or as rheology modifier.

It is further preferred that the method of the present invention and thepolymers of acrylamide are used in processes for solid liquid separationas for example flocculant or dewatering aid, which facilitatethickening, clarifying, filtration and centrifugation in order toenhance settling rates, to improve clarities and to reduce underflowvolumes. In particular, in filtration processes the polyacrylamide homo-or co-polymer of the present invention increase filtration rates andyields, as well as reducing cake moisture contents.

Further preferred is the use of the method and the obtainedpolyacrylamide of the present invention in particular for materialhandling and as binder. In the mining industry, the movement of largevolumes of material is required for processing the rock and/or oreswhich have been extracted from the deposits. The typical rock and/or oreprocessing for example starts with ore extraction, followed by crushingand grinding the ore, subsequent mineral processing (processing or thedesired/valuable mineral material), then for example metal productionand finally the disposal of waste material or tailings. It was asurprise that with the method of the present invention and in particularthe obtained polyacrylamide the handling of the mineral material can beenhanced by increasing efficiency and yield, by improving productquality and by minimizing operating costs. Particularly, the presentinvention can be used for a safer working environment at the mine siteand for reduction of environmental discharges. Preferably, the methodand the obtained polyacrylamide of the present invention can for examplebe used as thickener, as density and/or rheology modifier, for tailingsmanagement. The obtained polyacrylamide polymer can modify the behaviorof the tailings for example by rheological adjustment. The obtainedpolyacrylamide polymers are able to rigidify tailings at the point ofdisposal by initiating instantaneous water release from the treatedslurry. This accelerates the drying time of the tailings, results in asmaller tailings footprint and allows the released water to be returnedto the process faster. This treatment is effective in improving tailingsproperties in industries producing alumina, nickel, gold, iron ore,mineral sands, oil sands or copper for example. Further benefits of thepolymers obtained according to the present invention are for examplemaximized life of disposal area, slurry placement control, no re-workingof deposit required, co-disposal of coarse and fine material, fastertrafficable surface, reduced evaporative losses, increased volume forrecycling, removed fines contamination, reduced fresh water requirement,lower land management cost, less mobile equipment, lower rehabilitationcosts, quicker rehabilitation time, lower energy consumption,accelerated and increased overall water release, improved rate ofconsolidation, reduced rate of rise, reduced amount of post depositionalsettlement.

Preferably, the obtained product from the method of the presentinvention is used for agglomeration of fine particulate matter and forthe suppression of dust. Particularly, polyacrylamide polymers orcopolymers are used as organic binders to agglomerate a wide variety ofmineral substrates. For example, the polyacrylamide polymers orcopolymers are used for iron ore pelletization as a full or partialreplacement for bentonite. The product from the method of the presentinvention can be used as binder, in particular as solid and liquidorganic binders in briquetting, extrusion, pelletization, spheronizationand/or granulation applications and gives for example excellentlubrication, molding and/or binding properties for processes such ascoal-fines briquetting, carbon extrusion, graphite extrusion and/ornickel briquetting.

It is preferred that the method of the present invention and inparticular the aqueous polyacrylamide solution obtained by the method isused for the beneficiation of ores which comprise for example coal,copper, alumina, gold, silver, lead, zinc, phosphate, potassium, nickel,iron, manganese, or other minerals.

Advantages of the Process According to the Invention

The process according to the present invention provides significantadvantages as compared to known processes for the manufacture ofpolyacrylamide powders as well as compared to known processes formanufacturing polyacrylamide solutions on-site.

As already outlined above, drying aqueous polyacrylamide gel therebyobtaining polyacrylamide powders, transporting the powders to the siteof use and re-dissolving the dry powders at the site of use is energyextensive and consequently the operational costs for drying are high.Furthermore, also the capital expenditure for the entire post-processingequipment including size reduction, drying, sieving, grinding issignificant in relation to the total capital expenditure for the entireplant.

As compared to the known processes of manufacturing aqueouspolyacrylamide solutions on-site by polymerizing aqueous acrylamidesolutions and dissolving the gels obtained the process according to thepresent invention has the advantage that is easy to move the entireplant when polyacrylamide solutions are no longer needed at a location,i.e. at an oil well, but at another location, i.e. another oil well.

1.-46. (canceled)
 47. A process for producing an aqueous polyacrylamidesolution comprising polymerizing an aqueous solution comprising at leastacrylamide thereby obtaining an aqueous polyacrylamide gel anddissolving said aqueous polyacrylamide gel in water, characterized inthat the process is conducted in a modular, relocatable plant and theprocess comprises at least the following steps: [1] Preparing—in arelocatable monomer make-up unit—an aqueous monomer solution comprisingat least water and 5% to 45% by weight—relating to the total of allcomponents of the aqueous monomer solution—of water-soluble,monoethylenically unsaturated monomers, wherein said water-soluble,monoethylenically unsaturated monomers comprise at least acrylamide [2]Inerting and radically polymerizing the aqueous monomer solutionprepared in step [1] in the presence of suitable initiators for radicalpolymerization under adiabatic conditions, wherein the polymerization isperformed in a relocatable polymerization unit having a volume of 1 m³to 100 m³, the aqueous monomer solution before the onset ofpolymerization has a temperature T₁ not exceeding 30° C., and thetemperature of the polymerization mixture raises in course ofpolymerization—due to the polymerization heat generated—to a temperatureT₂ of at least 45° C., thereby obtaining an aqueous polyacrylamide gelhaving a temperature T₂ which is hold in the relocatable polymerizationunit, [3] removing the aqueous polyacrylamide gel from the relocatablepolymerization unit, [4] comminuting the aqueous polyacrylamide gel byconveying the aqueous polyacrylamide gel through at least onerelocatable comminuting unit, thereby obtaining aqueous polyacrylamidegel pieces, and [5] dissolving the aqueous polyacrylamide gel pieces inan aqueous liquid in a relocatable dissolution unit, thereby obtainingan aqueous polyacrylamide solution.
 48. The process according to claim47, wherein the acrylamide needed for the process is obtained byhydrolyzing acrylonitrile in water in the presence of a biocatalystcapable of converting acrylonitrile to acrylamide, thereby obtaining anaqueous acrylamide solution.
 49. The process according to claim 48,wherein the manufacture of acrylamide by hydrolyzing acrylonitrile inwater in the presence of a biocatalyst capable of convertingacrylonitrile to acrylamide is conducted at another location and theaqueous acrylamide solution is transported to the location of themodular, relocatable plant.
 50. The process according to claim 47,wherein the process comprises an additional step [0] comprisinghydrolyzing acrylonitrile in water in the presence of a biocatalystcapable of converting acrylonitrile to acrylamide in a relocatablebioconversion unit, thereby obtaining an aqueous acrylamide solution,and wherein said aqueous acrylamide solution is used for step [1]. 51.The process according to claim 47, wherein the relocatable monomermake-up unit comprises a double-walled monomer make-up vessel having avolume of 10 m³ to 150 m³ and means for controlling the temperature ofthe aqueous monomer solution.
 52. The process according to claim 47,wherein the relocatable polymerization unit has a volume from 5 m³ to 40m³.
 53. The process according to claim 47, wherein T₁ is from −5° C. to+5° C. and T₂ is from 50° C. to 70° C.
 54. The process according toclaim 53, wherein the monomer concentration is from 15 to 24.9% by wt.55. The process according to claim 47, wherein the relocatablepolymerization unit is a polymerization unit P1 comprising a cylindricalupper part having a length of 4 m to 6 m and a diameter from 1.5 m to2.5 m, a conical part at its lower end having a conus angle from 15° to90°, feeds for the aqueous monomer solution, a bottom opening having adiameter from 0.2 to 0.8 m for removing the polyacrylamide gel, andmeans allowing to deploy the unit P1 in a vertical manner.
 56. Theprocess according to claim 55, wherein the volume of the relocatablepolymerization unit P1 is from 20 m³ to 30 m³.
 57. The process accordingto claim 47, wherein the aqueous monomer solution is inerted byinjecting an inert gas into a monomer feed line connecting the monomermake-up unit with the relocatable polymerization unit and removing thegas using a degassing unit.
 58. The process according to claim 47,wherein the aqueous monomer solution is inerted by injecting an inertgas into a monomer feed line connecting the monomer make-up unit withthe relocatable polymerization unit and removing the gas from thepolymerization unit.
 59. The process according to claim 47, wherein theaqueous monomer solution is inerted in the relocatable polymerizationunit by bubbling an inert gas through the aqueous monomer solution. 60.The process according to claim 59, wherein the relocatablepolymerization unit is a polymerization unit P1 and the inert gas isintroduced into the aqueous monomer solution by nozzles in the conicalpart of polymerization unit P1 or an additional cylindrical sectionconnection the lower end of the conical section and the bottom opening.61. The process according to claim 47, wherein the aqueouspolyacrylamide gel is removed from the relocatable polymerization unitin course of step [3] by applying pressure onto the gel and pressing itthrough an opening in the polymerization unit, wherein pressure onto thegel is applied by means of gases, selected from the group of air,nitrogen, or argon and/or by means of aqueous fluids.
 62. The processaccording to claim 61, wherein a polymerization unit P1 is used, and theaqueous polyacrylamide gel is removed through the bottom opening. 63.The process according to claim 47, wherein in course of step [4] theaqueous polyacrylamide gel is conveyed through the relocatablecomminuting unit and an aqueous liquid is fed into the comminution unit,thereby yielding a mixture of pieces of aqueous polyacrylamide gel in anaqueous polyacrylamide solution.
 64. The process according to claim 47,wherein the relocatable comminution unit comprises means for comminutingaqueous polyacrylamide gels selected from static cutting devices, movingcutting devices, perforated plates, static mixers, water-jet cuttingdevices or combinations thereof.
 65. The process according to claim 47,wherein the relocatable comminution unit comprises at least onewater-jet cutting device.
 66. The process according to claim 47, whereina relocatable polymerization unit P1 is used and the relocatablecomminution unit (34) is connected with the bottom opening (32) of thepolymerization unit P1 and aqueous polyacrylamide gel is conveyed fromthe polymerization unit P1 through the comminution unit.
 67. The processaccording to claim 47, wherein the relocatable dissolution unitcomprises at least a dissolution vessel, at least one stirrer, means forfilling the dissolution unit with aqueous liquid and pieces of aqueouspolyacrylamide gel and means for removing aqueous polyacrylamidesolution.
 68. The process according to claim 67, wherein at least tworelocatable dissolution units are connected in series.
 69. The processaccording to claim 47, wherein the aqueous polyacrylamide solutionobtained in course of step [5] is transported from the site of themodular, relocatable plant to a site-of-use which is distant from thefirst location in a transport unit and removed from the transport unitat the site-of-use.
 70. The process according to claim 69, wherein theaqueous polyacrylamide solution transported in the transport unit is aconcentrate having a concentration of 2.1% to 14.9% by weight ofpolyacrylamides relating to the total of all components of theconcentrate.
 71. The process according to claim 69, wherein thesite-of-use is at an oil well.
 72. The process according to claim 47,wherein the modular, relocatable plant is deployed on an oilfield. 73.The process according to claim 47, wherein the modular, relocatableplant is deployed in a mining area.
 74. A modular, relocatable plant formanufacturing aqueous polyacrylamide solutions by polymerizing anaqueous solution comprising at least acrylamide thereby obtaining anaqueous polyacrylamide gel and dissolving said aqueous polyacrylamidegel in an aqueous liquid, comprising at least a relocatable storage unitfor an aqueous acrylamide solution, optionally relocatable storage unitsfor water-soluble, monoethylenically unsaturated monomers different fromacrylamide, a relocatable storage unit for polymerization initiators, arelocatable monomer make-up unit for preparing an aqueous monomersolution comprising at least water and acrylamide, a relocatablepolymerization unit for polymerizing the aqueous monomer solution in thepresence of polymerization initiators, a relocatable comminution unitfor comminuting aqueous polyacrylamide gel to pieces of aqueouspolyacrylamide gel, a relocatable dissolution unit for the dissolutionof pieces of aqueous polyacrylamide gel in aqueous fluids,
 75. Themodular, relocatable plant according to claim 74, wherein the plantadditionally comprises the following units: a relocatable storage unitfor acrylonitrile, a relocatable bioconversion unit for hydrolyzingacrylonitrile in water in the presence of a biocatalyst capable ofconverting acrylonitrile to acrylamide, a relocatable unit for removingthe biocatalyst from an aqueous acrylamide solution.